Theatomic masses, based on the exact number 12.00000 as the assigned atomic mass of the'-prir.

';*
cipal isotope of carbon, 12C, are the most recent (1961) values adopted by the International
Union of Pure and Applied Chemistry. The unit of mass used in this table is called atomic mass
Group—* I II ill IY
Period Series'
IH
I I 1.00797

3 Li 4 Be 5B 6C
2 2 6.939 9.0122 10.811 12.01115

11 Na 12 Mg 13 Al 14 Si
3 3 22.9898 24.312 26.9815 28.086

19 K 20 Ca 21 Sc 22 Ti
4 39.102 40.08 44.956 47.90
4
29 Cu 30 Zn 31 Ga 32 Ge
5 63.54 65.37 69.72 72.59

37 Rb 38 Sr 39 Y 40 Zr
6 85.47 87.62 88.905 91.22
5
47 Ag 48 Cd 49 In 50 Sn
I* 7 107.870 112.40 114.82 118.69
r^.
55 Cs 56 Ba 57-71 *72 Hf
m 132.905 137.34 Lanthanide 178.49
series*
6
79 Au 80 Hg 81 Tl 82 Pb
9 196.967 200.59 204.37 207.19

87 Fr 88 Ra 89-Actinide
7 10 [223] , [226.05] series**

‘ Lanthanide series: 57 La 58 0». 59 Pr 60 Nd 61 Pm 62 Sm

138.91 140.12-:' 140.907 144.24 [147] 150.35
** Actinide series: 89 Ac 90 Th ' * 91'Pa 92 U 93 Np 94 Pu
[227] 232.038 [231] , 238.03 [237] [242]

Table A—2 Fundamental Constants

Constant Symbol Value

Velocity of light C 2.9979 X IO8 m s” 1

Elementary charge € 1.6021 X 10~19 C
Electron rest mass me 9.1091 X 10“ 31 kg
Proton rest mass mp 1.6725 X IO"27 kg
Neutron rest mass Wn 1.6748 X IO-27 kg
Planck constant h 6.6256 X IO -*4 J s
h = h/2ir 1.0545 X IO"34 Js
Charge-to-mass ratio for electron e/me t 1.7588 X IO11 kg” 1
Quantum charge ratio h/e * 4.1356 X IO "15 J s (
Bohr radius oo v 5.2917 X I0~u m
,Compton wavelength:
of electron \c,e 2.4262 X IO -12 m
I of Protoni ^C,P 1.3214 X 10“ 15m
Rydberg constant B 1.0974 X IO7 Hi-1
 unit (amu); I amii “ 1.6604 X 10~27 kg. The atomic mass of carbon is 12.01115 on this scale
because it is the average of the different isotopes naturally present in carbon. (For artificially
produced elements, the approximate atomic mass of the most stable isotope is given in brackets.)
y vi V iI y in o

2 He
4.0026
7N 80 9F 10 Ne
14.0067 15,9994 ' 18.9984 20.183
15 P 16 S 17 Cl 18 A
30.9738 32.064 35.453 39,948

23 V 24 Cr 25 Mn 26 Fe 27 Co 28 Ni
50.942 51.996 54.9380 55.847 58.9332 58,71 '

33 As 34 Se 35 Br 36 Kr
74.9216 78.96 79.909 83.80

: 41 Nb 42 Mo 43 Tc 44 Ru 45 Rh 46 Pd
* 92,906 95.94 [99] 101.07 102.905 106.4

51 Sb 52 Te 53 1 54 Xe
121.75 127.60 126.9044 131.30

73 Ta 74 W 75 Re 76 Os 77 Ir 78 Pt
180.948 183.85 186.2 190.2 192.2 195.09

83 Bi 84 Po 85 At 86 Rn
208.980 [210] [210] [222]

63 Eu 64 Gd 65 Tb 66 Dy 67 Ho 68 Er 69 Tm 70 Yb 71 Lu
151.96 157.25 158.924 162.50 164.930 167.26 168.934 173.04 174.97
95 Am 96 Cm 97 Bk 98 Cf 99 Es 100 Fm 101 Md 102 No 103
[243] [245] [249] [249] [253] [255] [256]

Constant Symbol Value

Bohr magneton MB 9.2732 X IO" 24 J T " 1

Avogadro constant Na 6.0225 X IO23 mol" 1
Boltzmann constant k 1.3805 X IO -23J 0K " 1
Gas constant E 8.3143 J 0K " 1 mol" 1
Ideal gas normal volume (STP) V0 2.2414 X IO" 2 m3 mol” 1
Faraday constant F 9.6487 X IO4 C mol” 1
Coulomb constant Xe 8.9874 X IO9 N m2 C ” 2
Vacuum permittivity Co 8.8544 X IO -12N " 1 m" 2 C2
Magnetic constant Xm 1.0000 X 10” 7 m kg C " 2
Vacuum permeability MO 1.3566 X IO" 9 m kg C " 2
Gravitational constant 7 6.670 X l O " 11 N m 2 kg” 2
Acceleration of gravity at sea level and
at equator Q 9.7805 m s” 2
Numerical constants: * *• 3.1416; e » 2,7183; \/2 — 1.4142: \/ 3 1.7320
FUNDAMENTAL

ADDISON-WESLEY PUBLISHING C O M PA N Y
U N IV E R S IT Y PHYSICS

VO LU M E II I

Q U A N T U M A N D STATISTICAL P H Y S IC S

M A R CE LO ALO NSO

Department o/ Scientific Affairs, Organization of Am erican States

E D W A R D J. F IN N

Department of Physics, Georgetown University

R e a d in g , M a ss a c h u s e tts · M en lo P a r k , C a lifo rn ia
D o n M ills, O n ta rio · W o k in g h a m , F.ngland · A m s te rd a m · B o n n · S y d n e y
S in g a p o re · T o k y o · M a d rid · B o g o ta · S a n tia g o · S a n J u a n
 T H IS BOOK IS A N A D D IS O N -W E S L E Y
W O RLD STUDENT S E R IE S E D IT IO N

A com plete and unabridged reprint of the original Am erican textbook, this
W orld Student Series edition m ay be sold only in those countries to which it
is consigned b y Addison-W esley or its authorized trade distributors. I t may
not be re-exported from the country to which it has been consigned, and it
m ay not be sold in the United States of Am erica or its possessions.

T h e cover design o f this volum e is adapted from the August 1966 issue o f the
m agazine Am ericas, published b y the Pan Am erican U nion in Spanish, English,
and Portuguese; used b y special permission.

C op yrigh t (c) 1968 by Addison-W esley Publishing Com pany, Inc. AU rights
reserved. N o part of this publication m ay be reproduced, stored in a retrieval
system, or transm itted, in any form or b y any means, electronic, mechanical,
photocopying, recording, or otherwise, w ithout the prior w ritten permission
of the publisher. O r i g i n a l e d i t i o n p u b lis h e d in th e U n it e d States o f
A m e r i c a . P u b lis h e d s im u lt a n e o u s ly in C a n a d a . Philippines C opyright
1968.

Q R S T U V -D A -8 9 8 7 6
 FO RE W O RD

This book is the third and last volum e of a series published under the general title of
Fundamental University Physics. T h e purpose of this series is to offer to students of science
and engineering a logical and unified presentation of physics at the introductory under­
graduate level, w ith emphasis on the basic ideas which form the core of physics: the
conservation laws, the interrelation between particles and fields, and the atom ic vie w of
m atter. W e have tried to present physical concepts in such a w ay th at the student w ill
attain a clear understanding of their theoretical m eaning and recognize their experim ental
foundations, noting the close interrelation between th eory and experim ent. W e also have
tried to develop in the student the ab ility to manipulate the mathem atics required for
the expression o f such concepts. T h e three volum es cover the equivalent of a two-sem ester
course in general physics plus a one (or tw o ) semester course in modern physics. Volum e
I treats mechanics and the gravitation al interaction. Volum e I I deals w ith electrom agnetic
interactions and waves. V olu m e I I I covers quantum and statistical physics (including
therm odynam ics). A lth ou gh the three volum es are closely related and follo w a logical
sequence, each one is self-contained and can be used independently of the others. T his
is particularly true of Volum e I I I , which covers m ost of the subject m atter usually in­
cluded in an introdu ctory modern physics course.
T h e curricula for all sciences are under great pressure to incorporate new subjects th at
are becom ing more relevant. W e expect th at this series w ill relieve this pressure b y raising
the level of the student’s understanding of physical concepts and his ab ility to apply them
to concrete situations. T his w ill perm it m any interm ediate courses presently offered in
the undergraduate curriculum to be upgraded. T h e tradition al undergraduate courses
in mechanics, electrom agnetism , and modern physics w ill benefit m ost from this upgrading.
Thus the student w ill finish his undergraduate career at a higher level of knowledge than
form erly: an im portant benefit for those who term inate their form al education at this
point. A lso there w ill now be room for newer and m ore exciting courses at the graduate
level. T his same trend is found in the more recent basic textbooks in other sciences for
freshman and sophomore courses.
T h e first part of this volum e is called Quantum Physics. Quantum ideas are the essence
of to d a y ’s physics. U n fortunately, except for a brief introduction to B ohr’ s ideas and to
w ave-particle du ality in the introdu ctory general physics course, there has often been a
delay in exposing students to quantum -m echanical concepts and their applications.
T ra d ition a lly on ly the physics and chem istry m ajors learned quantum mechanics, and
then rarely before the senior year. H ow ever, physics and chem istry majors should acquire
a w orking knowledge of quantum ideas as early in their curricula as possible so th at
Pt Foreword

they may utilize this knowledge in subsequent undergraduate courses. This procedure
is strongly endorsed by the Commission on College Physics. Present trends in biology
and engineering demand that students in these fields also have a basic understanding of
the solid state and of molecular structure. Therefore we have been careful to introduce
the student to quantum mechanics in a way which, although elementary, allows him to
apply quantum concepts to different situations.
Chapter I is an introduction to the foundation of quantum ideas. This is followed in
Chapter 2 by the necessary background in quantum mechanics; here we emphasize the
way in which physical information about a system is extracted from the shape of the
potential-energy function and a knowledge of the general nature of wave functions. In
the succeeding chapters, 3 through 9, quantal concepts and techniques are applied to the
analysis of atoms, molecules, solids, nuclei, and fundamental particles.
In the second part of the text (designated Statistical Physics), we use statistical methods
to consider the properties of matter in bulk. Like quantum mechanics, statistical physics
is a well-founded, powerful tool, to which the student should be introduced as early as
possible. After discussing classical statistical mechanics in Chapter 10, we present thermo­
dynamics from a statistical point of view in Chapter 11 and apply it to both ideal and
real gases in Chapter 12. We are firmly convinced that this is the most appropriate method
to follow in introducing the student to the concepts of thermodynamics. The text ends
with a brief introduction to quantum statistics in Chapter 13.
Since many students now learn the basic ideas of relativity in their general physics
course, the special theory of relativity is discussed in the appendix. (A more complete
discussion of relativity appears in Volumes I and I I of the series.) Several collateral
topics, such as group velocity and the methods of particle detection, are also discussed
in the appendix.
We have kept the mathematical requirements within the topics covered by a standard
calculus course. We have also often either omitted or relegated to the problem sections
those mathematical calculations which are not essential to an understanding of the main
trend of physical ideas; one example of such calculations is the sometimes boresome task
of finding certain solutions to Schrodinger’s equation.
Many applications of the fundamental principles, as well as the discussion of a few
more advanced topics, appear in the form of worked examples. The text has been written
so that the student may omit all examples at his first reading. During a second reading
the student should consider those examples chosen by the instructor. The instructor may
discuss these examples at his convenience or propose them on a selective basis. Certain
sections of the text may be omitted without loss of continuity. The problems at the end
of each chapter follow the sequence of the chapter, with a few more difficult problems at
the end. The large number of varied problems means that the instructor can choose
problems to match the abilities of his students. Hence by proper selection of the material
in this text, the instructor can adapt the text to a one- or two-semester course and at the
same time give the student both a challenge and a motivation to meet that challenge.
We want to express our gratitude to all those who, by their assistance and encourage­
ment, have made this work possible. We recognize in particular Professor David Lazarus,
whose comments and criticisms helped to improve many aspects of the text. Last— but
not least-—we thank our wives, who have so patiently stood by us.

Washington, D. C. Marcelo Alonso

January 1968 Edward J. Finn
 CONTENTS

P A R T I Q U A N T U M P H Y S IC S

^ C h a p te r I T h e F o u n d a tio n s o f Q u a n tu m Physics

Introduction 4 □ Electromagnetic radiation 4 (5 Blackbody

radiation 7 □ Photoelectric emission 11 O ' Scattering of radiation
by free electrons 14 □ Photgns 18 □ Stationarystates 22 □
Experimental evidence of stationary states 26 □ Interaction of
radiation with matter 29 □ Particles and fields 33 □ Particles
and wave packets 38 □ Heisenberg’s uncertainty principle for
position and momentum 39 □ The uncertainty relation for time
and energy 43

C h a p te r 2 Q u a n tu m M ech an ics

Introduction 53 □ W a vefu n ction a n d p rob ab ilityd en sity 53 □

Schrodinger’s equation 56 □ Potential step 59 □ ' Particle in a
potential box 63 □ The harmonic oscillator 71 □ Energy levels
and wave functions in general 75 □ Potentialbarrierpenetration 80 □
Symmetry, wave functions, and parity 88 □ The time-dependent
Schrodinger equation 90 □ Transition probabilities and selection
rules 94 □ The formal theory of quantum mechanics 96

C h a p te r 3 A to m s w ith O n e Electron

Introduction 109 □ T h eh yd rogen atom 109 □ T h esp ectru m of

hydrogen 115 □ Quantizationofangularm om entum 117 □
One-electron wave functions under central forces 121 □ The
Zeeman effect 132 □ Electron spin 135 □ Addition of angular
momenta 137 □ Spin-orbit interaction 139

j Cha pt e r 4 A to m s w ith M a n y E lectrons

Introduction 150 □ T h eh eliu m ato m 150 □ Theexclusion

principle 158 □ E lectronicstru ctureofatom s 161 □ L-S
coupling 164 □ Atoms with one or two valence electrons 171 □
X-ray spectra 176
titi
v iii Conlenls

C h a p te r 5 M olecules

Introduction 183 □ The hydrogen molecule ion 183 □

Molecular orbitals of diatomic molecules 191 □ Electronic
configuration of some diatomic molecules 194 □ Polyatomic
molecules 202 □ Conjugated molecules 208 □ Molecular
rotations 212 □ Molecular vibrations 215 □ Electronic transitions
in molecules 222 □ Conclusion 225

C h a p te r 6 Solids

Introduction 231 □ Types of solids 231 □ Band theory of solids

243 □ Free-electron model of a solid 246 □ Electron motion in
a periodic structure 251 □ Conductors, insulators, and semiconductors
261 □ Quantum theory of electrical conductivity 268 □ Radiative
transitions in solids 274

C h a p te r 7 N u c le a r S tru c tu re

Introduction 283 □ Isotopes, isotones, and isobars 283 □ The

atomic mass unit 286 □ Properties of the nucleus 286 □ Nuclear
binding energy 293 □ Nuclearforces 298 □ T h e g ro u n d s ta te o f
the deuteron 301 □ Neutron-proton scattering at low energies
303 □ The shell model 310 □ Nuclear radiative transitions 319

C h a p te r 8 N u c le a r Processes

Introduction 329 □ Radioactive decay 329 □ Alpha decay

335 □ Beta decay 340 □ Nuclear reactions 348 □ Nuclear
fission 357 □ Nuclear fusion 363 □ The origin of the elements 367

C h ap ter 9 F u n d a m e n ta l P articles

Introduction 377 □ Particle genealogy 378 □ Particles and

antiparticles 379 □ Particle instability 386 □ The conservation
laws 397 □ Invariance, symmetry, and conservation laws 403 □
Resonances 414 □ What is a fundamental particle? 419

P A R T 2 S T A T I S T I C A L P H Y S IC S

C h a p te r IO E lassical S tatistical M ech an ics

Introduction 434 Statistical equilibrium 434 @ The

Maxwell-Boltzmann distribution law 436 Jg Temperature 443 □
Thermal equilibrium 448 @ Application to the ideal gas 450

C h a p te r 11 T h e rm o d y n am ics

Introduction 462 □ Conservation of energy of a system of

particles 462 □ Many-particle systems: work 464 □
 Contents ix

Many-particle systems: heat 466 □ The first law of thermodynamics

467 □ Graphical representation of processes 469 □ Special
processes 473 □ Entropy and the second law of thermodynamics
475 □ Entropy and heat 4S0 □ Discussion of processes in terms
of entropy 484

C h a p te r 12 T h e rm a l Properties o f G ases

Introduction 494 □ The equation of state of an ideal gas 494 □

Equation of state for real gases 497 □ Heat capacity of an ideal
monntomic gas 504 □ Heat capacities of an ideal polyatomic gas
506 □ The principle of equipartition of energy 512

C h ap ter 13 Q u a n tu m Statistics

Introduction 519 □ Fermi-Dirac distribution law 519 □ The

electron gas 522 □ Application of Fcrmi-Dirac statistics to electrons
in metals 526 □ Bosc-Einstein distribution law 528 □ The photon
gas 531 □ Heat capacity of solids 536 □ The ideal gas in
quantum statistics 540

Appendixes

I Relativistic mechanics 551 □ I I Collisions 555 □ I I I Group

velocity 560 □ IV Some useful integrals 562 □ V Stirling’s
formula 563 □ V I Lagrange’s undetermined multipliers 564 □
V I I The detection of particles 564

T ab les 577

L i s t o f TahIcs 581

A n sw ers to O d d -N u m b e re d P ro b le m s 583

Index 589
 PART I
QUANTUM PHYSICS

i The Foundations o f Quantum Physics

2 Quantum Mechanics
3 Atoms with One Electron
U Atoms with M any Electrons
5 Molecules
6 Solids
7 Nuclear Structure
8 Nuclear Processes
9 Fundamental Particles
2

One o f the fundam ental ob jectives o f physics is to an alyze the properties o f th e

basic com ponents o f m atter and the processes th at occur am ong them as a result
o f th eir interactions. T hese basic com ponents— called fundam ental or elem en ta ry
p articles— are electrons, protons, neutrons (and others) which group to geth er to
form nuclei, atoms, and molecules. These groups, in turn, com bine to form m a tte r
in bulk. A lth ou gh the m otion o f fundam ental particles com plies w ith the prin­
ciples o f conservation o f m om entum , angular m om entum , and energy, th e a n a ly ­
sis o f this m otion requires a fram ew ork d ifferent in several respects from the one
developed in classical (o r N ew to n ia n ) mechanics fo r the analysis o f m acroscopic
m otion. T h is m ore refined th eory is called quantum mechanics. W e m ust under­
stand it w ell before we em bark on a discussion o f atom s, molecules, and nuclei.
F ortu n ately, atom s and m olecules are essentially the result o f electromagnetic in ter­
actions betw een the p ositively charged nuclei and the n eg a tively charged electrons.
Thus w e can discuss atom s and molecules, w ith ou t havin g to appeal to oth er less-
well-understood forces, b y com bining the laws o f electrom agnetism w ith those o f
quantum mechanics. T h e sam e technique m ay also be used for gases, liquids, and
solids. On the other hand, nuclei are basically the result o f a new ty p e o f force, the
so-called strong or nuclear interaction. Since the strong interaction is not y e t well
understood, its analysis is much m ore involved . C onsequently, in this te x t our
discussion o f nuclei must be o f a m ore d escriptive nature.
Perhaps the m ost dynam ic and stim ulating field o f con tem porary physics is the
study o f the fundam ental particles. T h e interactions observed betw een these par­
ticles require the introduction o f another ty p e o f force, in ad dition to th e stron g
interaction. T h is force is called the weak interaction. A n oth er force, the gravita­
tional interaction, w hich is the w eakest o f all interactions, plays a lesser role insofar
as the basic structure o f m atter is concerned.
T h e rela tive value o f the four interactions is:

Strong I
E lectrom agnetic IO-2
W eak ΙΟ" 13
10-38
G ravitatio n al

T h e processes in v o lvin g fundam ental particles h ave m otivated a new form alism ,
som ewhat d ifferent from quantum mechanics, called quantum field theory. T h is
theory, how ever, is too com plex to be considered in this text.
 I
THE FOUNDATIONS OF
QUANTUM PHYSICS

1.1 Introduction
1.2 Electromagnetic Radiation
1.3 Blackbody Radiation
IA Photoelectric Em ission
1.5 Scattering o f Radiation by Free Electrons
1.6 Photons
1.7
1.8 E xperim ental Evidence o f Stationary States
1.9 Interaction o f Radiation with M atter
1.10 Particles and Fields
1.11 Particles and Wave Packets
1.12 Heisenberg's Uncertainty P rin c ip le
Position and Mom entum
1.13 The Uncertainly Relation fo r T im e and Energy
«Ρ —

U The foundations o f quantum physics ( 1.2

1.1 ln trod u vtion

B y the end o f the nineteenth century, and during the first quarter o f the tw entieth,
experim ental evidence began to accum ulate which indicated th at the interaction o f
electrom agnetic radiation w ith m atter was n ot en tirely in accordance w ith the IqMis
o f electrom agnetism . T h ese laws w ere the result o f the w ork o f Am pbre, Laplace,
F araday, H en ry, M axw ell, and m any others, and are synthesized in M a x w e ll’s
equations for the electrom agnetic field. A t the same tim e the th eory o f the atom ic
structure o f m atter was developin g, m ainly as a result o f the discovery o f the elec­
tron and the confirm ation o f the nuclear m odel o f the atom . S till another series o f
experim ents forced the physicist to review his concepts o f the m otion o f subatomic
particles, since th ey app aren tly did not m ove precisely in accordance w ith the
assumptions o f N ew ton ian mechanics. T o explain the new observations, a sequence
o f new ideas, introduced in a m ore or less acl hoc fashion, were incorporated b y sev­
eral physicists. W ith the passage o f tim e, and by the efforts o f m any brillian t men,
these ideas e v olved until th ey becam e w hat is now known as the quantum theory, a
th eory which is, perhaps, the essence o f con tem porary physics. In this chapter we
shall review the m ore im portant experim ental bases o f quantum physics.
Y

F ig. 1-1. Electric field of a charge at rest. F ig . 1-2. E lectrican dm agneticfieldsof

a uniformly moving charge.

1.2 E ivvt rom a gn vtiv H ndiation

T h e electrom agnetic interaction between tw o charged particles can best be de­
scribed in terms o f the concepts o f electric and m agnetic fields produced b y the
charges. W h en a charged p article is a t rest rela tiv e to an inertial observer, the
observer measures a field which is called the electric field o f the charge (F ig . 1-1).
H ow ever, if the charge is in m otion rela tive to the observer, he observes a different
field, called the electrom agnetic field o f the charge (F ig . 1-2). One com ponent o f
the field is still called electric, while the rem aining com ponent is called the m agnetic
field. Such fields depend on the v e lo c ity and acceleration o f the charge rela tive to
the observer. Since the separation o f the field produced b y a charge into an elec­
tric and a m agnetic part depends on the rela tive m otion o f the charge and the ob­
server, w e should speak on ly o f the electrom agnetic field o f the charged particle.
C onversely, when a particle m oves through the electrom agnetic field produced by
1.2) Electromagnetic radiation 5

other charges, it experiences a force given by

F = g (€ + I-· x (B),

where ε and ® are the electric and m agnetic fields, respectively, as measured b y
an observer w h o measures the v e lo c ity o f the particle as v. In this w ay w e can
describe the electrom agnetic interaction o f charged particles in terms o f fields.
E n ergy is required to set up an electrom agnetic field. T h e energy per unit volum e
o f an electrom agnetic field in vacuum is

( 1. 1)

where « 0 and g o arc the vacuum p e rm ittiv ity and perm eab ility, respectively.
T h e energy o f a static electrom agnetic field (th a t is, a field th at does not change
w ith tim e) ob viou sly remains constant. H o w ever, when the field is time dependent,
the electrom agnetic energy at each point changes w ith tim e. T h e tim e variation s
o f an electrom agnetic field g iv e rise to an electrom agnetic w ave which propagates
w ith a v e lo c ity

c = ! / V i 0Mo « 3 X IO8 m s ~ \ (1.2)

which is the same as the v e lo c ity o f light in vacuum. W c m ay say th at the w a v e
carries the energy o f the electrom agnetic field. T h is energy which is carried b y an
electrom agnetic w a v e is som etimes called electromagnetic, radiation.
Since a charge a t rest relative to an observer produces a static field, the charge
does not radiate electrom agnetic energy. A lso it can be shown th at a charge which
is in uniform rectilin ear m otion does not radiate electrom agnetic energy because
the total energy o f its electrom agnetic field remains constant. A v e ry different
situation exists for a charge which is in accelerated m otion. T h e total energy o f the
electrom agnetic field o f an accelerated charge varies w ith tim e. T h erefore

an accelerated charge radiates electromagnetic energy.

T h e rale o f energy radiation by a charge q m ovin g w ith v e lo c ity i> and acceleration
a, when the v e lo c ity is small rela tive to the v e lo c ity o f light, is

(1.3)

One im portant conclusion is that, if a charge is to be m aintained in accelerated

m otion, energy must be supplied to com pensate for the energy transferred as radia­
tion. T h is means th at when an ion is accelerated, for exam ple in a V an de G raaff
accelerator or in a cyclotron, a fraction o f the energy supplied to the ion is lost as
electrom agnetic radiation. T h is en ergy loss, however, is negligible except at. rela-
tivistic energies. C harged particles trapped in the earth ’s m agnetic field, in sun
spots, or in distant celestial bodies such as the Crab nebula also em it radiation,
called synchrotron radiation. T h is radiation extends from radio frequencies to the
extrem e ultraviolet.
6 The foundations of quantum physics (1.2

I f the p article is decelerated instead o f being accelerated, E q . (1.3) still holds and
the energy radiated is th at excess which th e electrom agnetic field has as a result o f
th e decrease in the v e lo c ity o f the charge. F o r exam ple, when a fast charge such as
an electron or a proton hits a target and is stopped, a substantial p art o f its total
energy goes o ff as radiation (F ig . 1 -3). T h is radiation is called deceleration radia­
tion, or m ore com m only bremsstraldung (from the Germ an words Brem sung (decel­
eration ) and Strahlung (rad iation )]. T h is is the chief m echanism by which radiation
is produced in the x-ray tubes which are used in physical, m edical, and industrial
applications.

T h e energy radiated b y a charged particle m ay be absorbed b y oth er charged

particles which are subject to the action o f the electrom agnetic field produced by
the first particle. H en ce w e m ay describe the interaction o f tw o charged particles
as an exchange o f energy b y means o f emission and absorption o f radiation. For
example, the oscillating electrons in the antenna o f a radio broadcasting station
radiate energy. P a rt o f this energy is absorbed b y the electrons in th e antenna o f a
radio receiver, which results in a signal a t the receivin g station.
A n analysis o f the processes o f emission and absorption o f radiation (th a t is, the
interaction o f radiation and m a tte r) is fundam ental for understanding the behavior
o f m atter. A s w e shall see in th e follow ing sections, quantum physics evolved as a
result o f the analysis o f such processes.

E X A M P L E 1.1. The rate at which energy is radiated by an oscillating electric dipole.

S o lu tio n : Consider a charge q moving along the Z-axis in such a way that at any time
its position is given by z = z0 cos cot. This corresponds to an oscillatory motion of ampli­
tude zo and angular frequency ω. Thus the charge is equivalent to an oscillating electric
dipole. The acceleration of the particle is a = —ω2ζ. Substituting this value of a in
Eq. (1.3), we have
 Iilackbody radiation 7

The rate of energy radiation oscillates because of the variation of 2 with time. T o obtain
the average rate of energy radiation, we recall that (22) » vο = £20· Thus

(d lA = q2Zpoii . .
\ dl ) avo 12xtoC3

We may say that an oscillating electric dipole radiates energy at an average rate given by
Eq. (1.5) and that the radiation corresponds to an electromagnetic field oscillating with
the same frequency as the dipole.

K ( x)

F ig. 1-t. Monochromatic energy

density of blackbody radiation at
different temperatures as a function
of the frequency.

!•'requeney v

Φ # ..? Itla r lib o tly H a tlia iio n

Consider a c a v ity whose walls are"at a certain tem perature. T h e atom s com posing
the w alls are em ittin g electrom agnetic radiation; at. the same tim e th ey absorb
radiation em itted b y other atom s o f the walls. T h e electrom agnetic radiation field
occupies the w hole ca vity . W hen the radiation trapped within the c a v ity reaches
equilibrium w ith the atom s o f the walls, the am ount o f energy em itted by the
atom s per unit tim e is equal to the am ount absorbed b y them. Hence, when the radi­
ation in the c a v ity is a t equilibrium w ith the walls, the energy density o f the
electrom agnetic field is constant. E xperim ent has shown that, at equilibrium ,
the trapped electrom agnetic radiation has a well-defined energy distribution; that
is, to each frequency there corresponds an energy density which depends solely on
the tem perature o f the walls and is independent o f th eir m aterial. T h e energy
density corresponding to radiation w ith frequency between v and v - f dv is w ritten
e (i') dv, where E (g) is the energy density per unit frequency range, som etimes
called monochromatic energy density. T h e observed variation o f E(V) w ith the fre­
quency v is illustrated in Fig. 1-4 for tw o temperatures.' C u r v e s lik e th e s e w e r e
first obtained experim entally by Lum m er and Pringsheim in 189!). It m ay be
seen from th e curves th at for each tem perature the energy density shows a p ro­
nounced m axim um a t a certain frequency. N o te also th at the frequency a t which
the energy d ensity is maxim um increases as the tem perature increases. T h is ex­
plains the change in color o f a radiating b od y as its tem perature varies.
8 The foundations of quantum physics U .3

I f a sm all hole is opened in one o f the walls o f the ca v ity , some o f the radiation
escapes and m ay be analyzed. T h e hole appears v e ry bright when the body is a t
high tem peratures and the inten sity o f the equilibrium radiation within the c a v ity
is high, but it appears com pletely black at low tem peratures, when the intensity
o f the equilibrium radiation is negligible in the visible region o f the spectrum .
F o r th at reason the radiation com ing ou t o f the c a v ity was called blackbody radia­
tion by those who analyzed it in the nineteenth century.
T h e problem o f finding w h at mechanism causes radiating atom s to produce the
observed energy distribution o f blackbody radiation led to the birth o f quantum
physics. B y the end o f the last century all attem pts to explain this energy distribu­
tion using the concepts availab le a t th at tim e had failed com pletely. T h e Germ an
physicist .Max P lanck ( 1858-1947) suggested, abyut 1900, th at if the radiation in
th e c a v ity was in equilibrium w ith the atom s o f the walls, there should be a cor­
respondence between the energy distribution in the radiation and the energies of
the atom s in the ca vity . A s a m odel for the radiating atom s, Planck assumed that
atom s behave as harmonic oscillators, and th at each one oscillates w ith a given
frequency v. A s a second assumption Planck suggested that

each oscillator can absorb or emit radiation energy only in an amount

proportional to its frequency v.

T h is la tter condition is not required b y the classical theory o f electrom agnetism

(as expressed by M a x w e ll’s equations), which perm its a continuous emission or
absorption o f energy. G iven th at E is the energy absorbed or em itted in a single
process o f interaction o f an oscillator w ith electrom agnetic radiation, P lan ck ’s
assumption states that

E = hv, ( 1.6)

where h is a p rop ortion ality constant assumed to be the same for all oscillators.
Hence, when an oscillator absorbs or emits electrom agnetic radiation, its energy
increases or decreases b y an am ount hv. E quation (1.6) then im plies that

the energy o f atomic oscillators is quantized.

T h a t is, the energy o f an oscillator o f frequency v can attain on ly certain values,

which are (assuming th at the m inim um energy o f the oscillator is zero) 0 , hv, 2hv,
3hv, . . . . Thus, in general, the possible values o f the energy o f an oscillator o f fre­
quency v are

® En = nhv, (1.7)

where n is a p ositive integer. A s w e know, the energy o f an oscillator is propor­

tional to the square o f its am plitude and, a p rio ri, by properly adjusting the am pli­
tude o f the oscillations, w e can m ake an oscillator o f a given frequency have any
a rb itra rily chosen energy. T h erefo re P lan ck ’s idea was an ad hoc assumption which
could not be explained b y means o f classical concepts; it w as justified on ly because
 1.3) Blackbody radiation .9

it “w o rk e d ,” and because physicists a t the tim e lack ed a b e tte r explanation. W e

still do n o t liave a b etter explanation; w e must a c c e p t the quantization o f some
physical quantities as a fundam ental fact o f nature.
B y ap p lyin g some considerations o f a statistical n a tu re, togeth er w ith E q . (1.6),
Planck obtained, for th e energy density in b la c k b o d y radiation, an expression o f
the form

e W (L8)

where k is B oltzm an n ’s constant. T h is expression, w h ich agrees surprisingly well

w ith the experim ental values o f e ( c ) a t d ifferent tem peratures, has been accepted
’ as the correct expression fo r blackbody radiation. It is called P la n ck ’s radiation law.
A n interesting aspect is th at P lan ck ’s derivation c a n n o t presently be considered
as physically sound (which is the reason w e have o m itte d it). In other words, the
problem which precipitated the birth o f the qu an tu m th eo ry was first solved by
means o f an unsatisfactory m ethod. T h e problem had to w a it several years until
the quantum th eory was developed along other lines o f th ou ght before an adequate
m ethod o f calculation was found. T h is revised d e riv a tio n w ill be given in Sec­
tion 13.6. H o w ever, P lan ck ’s ideas, especially E qs. ( 1.6 ) and (1 .7), prom pted new
thinking b y m any other physicists w ho w ere w orking on th e interpretation o f other
related phenom ena; this led to rapid developm en t o f quantum theory.
In E q . (1.6) w e introduced an arb itrary constant li, called P la n ck ’s constant. Its
value, obtained b y m aking E q. ( 1 . 8 ) f i t the exp erim ental results for e ( c ) , is

I, = 6.6256 X IO" 34 J s. (1.9)

P lanck’s constant is one o f the m ost im portant con stants in physics.

E X A M P L E 1.2. Express the ,monochromatic energy density of blackbody radiation in

terms of wavelength.

S o lu tio n : Sometimes it is preferable to express the monochromatic energy density in

terms of wavelength instead of frequency. We define Ε ( λ ) according to the relation
E (X ) d\ = - E (V ) d r. We introduce the minus sign because d\ and d v have opposite
signs, although E (r ) and E (X ) are both positive. Thus, since v = c/ λ , we have

dv/dk cfk 2
and
E (X ) = — E (r ) dv/dk = E(i<)c/X2.

Replacing E(r) by the value given it in Eq. (1.8) and setting v = c/λ, we finally obtain

gW - g^A rC »■
, /»*—
— I
· (uo)

The graph of E(X) is shown in Fig. 1-5 for different temperatures. I t shows a pronounced
peak at a wavelength which depends on the temperature.
10 The foundations o f quantum physics

ε(λ)

W u v clen g tli λ

F ig. 1-5. M onochrom atic energy density of blackbody radiation at different tempera­
tures as a function of the wavelength.

E X A M P L E 1.3. Find the wavelength at which the monochromatic energy density of

blackbody radiation is maximum at a given temperature.

S o lu tio n : L et us use E q . (1.10) and, to simplify our exposition, we shall set x = hc/\kT,
s o that E (X ) becomes

8 ir ) f c V X5
E (X ) =
4,4 x
c h e

T o find the maximum of E(X), we first find d E / d x and equate it to zero. The resulting
equation is
e- ' + £ x — I = 0.

This is a transcendental equation, which we solve by successive approximation to obtain

x = 4.9651. Thus XT' = 6, where

h = hc/4 M o\k = 2.8978 X 10~ 3 m °K

is called the HTen d is p la c e m e n t co n sta n t. The expression

XT = b (1.11)

constitutes HTen’s d is p la c e m e n t la w , discovered 1896 b y Wilhelm Wien. This law states

that the maxima of E(X) at different temperatures T i , To, Ts, . . . fall at wavelengths
Xi, X2, Xe, . . . such that

X 1T 1 = X2T 2 = X3T 3 = · · · .
 Photoelectric emiss ion I1

We observe that, as the temperature of the body increases, the peak of its energy dis­
tribution is displaced toward shorter wavelengths, which causes a color change in the body.
Wien’s displacement law is thus very useful in determining the temperature of hot bodies,
such as ovens or stars, by finding the wavelength for which the intensity of the radiation
is a maximum.
W ien’s law also gives a method for measuring h in terms of the experimental value of b
and its definition in terms of Iil c, and k given above. The consistency of the results with
other measurements of h is another proof of the correctness of Planck’s distribution law.

E X A M P L E 1.4. Obtain the total energy density of blackbody radiation as a function

of temperature.

S o lu tio n : Since e(i<) dv is the energy density in the frequency range dr of the blackbody
radiation, the total energy density is

It is obvious that E is equal to the area under the curve E(r) of Fig. 1-4. Introducing the
variable x = hv/kT, we have dv — (kT/h) dx, and

_ S ir h ik fY Γ X3 dx
E — ^7r^i
c3 \ h ) Jo cx — I

The value of the integral is 6.4938, and thus

E = a T 4, ( 1- 12)
where
a = 51.95047rtt4/c3A3 = 7.5643 X I O - 16J m - 30K - 4.

Equation ( 1.12) is known as the Slefan-Iioltzmann law, discovered empirically in 1879 by

Josef Stefari and proved theoretically Uy Ludwig Boltzmann some years later, using
thermodynamical methods. Λ calculation, which will be omitted, shows that the energy
emitted by a blackbody per unit area and per unit time, called its radiation emittance, is
given by F = aT*, where σ = (:j)ca = 5.6693 X IO-8 W m ~ 2 0K -4 is called the Stefan-
Boltzmann constant.
The dependence of E or F on T 4 has been verified experimentally. From the measured
value of a or a we can recalculate h, again obtaining a consistent value. We can use the
Stcfan-Boltzmann law to determine the temperature of a blackbody by measuring its
radiation emittance.
I t should be noted that most radiating bodies— such as the sun, an incandescent fila­
ment, or a hot gas— do not behave like blackbodies, and therefore do not rigorously
obey the relations derived in this section.

δ/. Ι I tIioiovIftvtrift EmiHHion

In 1887, w h ile investigating the electric discharge between tw o electrodes as a
source o f electrom agnetic waves, H einrich H e rtz observed that the inten sity o f
the discharge was increased when the electrodes w ere illum inated w ith u ltraviolet
light. T h is effect suggested th at electrons w ere em itted from the illum inated sur­
12 The f OUiidalions of quantum physics (1 A

faces. A y ea r la te r W ilh elm H allw ach s observed an electronic emission when he,
illum inated the surfaces o f certain m etals such as zinc, rubidium, potassium, an<f
sodium. T h e process b y which electrons are released from a m aterial under the
action o f radiation is called photoelectric emission or photoelectric effect. T h e em itted
electrons are called photoelectrons because o f th e m ethod o f their production. T h e
electronic em ission increases w ith an increase in the intensity o f the radiation fall­
ing on the m etal surface, since m ore energy is availab le to release electrons; but a
characteristic dependence on the frequency o f the incident radiation is also ob­
served. T h is means that for each substance there is a minimum, or threshold,
frequ en cy v 0 o f electrom agnetic radiation such that, no m atter how intense the
radiation m ay be, no photoelectrons are produced for radiation o f frequency less
than v0. T h e photoelectric current as a function o f the frequency o f the incident
electrom agnetic radiation is shown in Fig. 1-6.

F ig. 1-6. Photoelectric current as a

function of the frequency of the incident
radiation.

In a m etal there are electrons which are m ore or less free to m ove throughout the
crystal lattice. These electrons do not escape from the m etal at normal tem pera­
ture because they do not have enough energy to overcom e the coulomb potential
energy at the surface o f the m etal. One w ay to increase the energy o f the electrons
is b y heating the m etal. T h e “eva p ora ted ” electrons are then called thermoelectrons.
T h is is th e kind o f electronic emission th at exists in electron tubes. H ow ever, as
the experim ents o f H ertz and H allwachs show, an oth er w ay to release electrons
from a m etal is to m ake it possible for the electrons to absorb energy from electro­
m agnetic r a d ia tio n .. Let us designate the energy required by an electron to escape
from a given metal by φ. Th en , given th at the electron absorbs an energy E , the
difference E — φ w ill appear as kinetic energy E s o f the escaping electron. H ence
w e m ay w rite

Ek = E - φ. (1.13)

O bviou sly if E is smaller than Φ no electronic emission w ill result.

In 1905 A lb e rt Einstein proposed an explanation fo r the dependence o f p h o to­
electric emission on the frequency o f the radiation. Einstein suggested th at free
electrons, in their interaction w ith electrom agnetic radiation, behave in the same
w ay P lan ck proposed for atom ic oscillators in connection w ith blackbody radia­
tion. Thus, according to Eq. ( 1.6), the energy E absorbed by an electron in a single
process from electrom agnetic radiation o f frequency v is E = hv. T h erefo re we
 Photoelectric emission 13

m ay w rite E q. (1.13) as

Ek = hv - φ. (1.14)

N o t all electrons require the same energy φto escape fro m th e m etal. W e call
the m inimum energy value φ 0 the work fu n ction o f the m etal. T h e n the m axim um
kinetic energy o f the escaped electrons is

E k, max = hv — φ0. (1.15)

From this equation w e see that, a t the frequency v0 f ° r which

hv ο — Φο = 0 or V0 = Φο/h,

the m axim um kinetic energy o f the electrons is zero. T h erefo re V0 is the m inim um
or threshold frequency a t which there is photoelectric emission. F o r frequencies
smaller than v0, so th at hv < φ0, there is no emission a t all, since the electrons can­
not absorb enough energy in a single process to escape from the m etal, regardless o f
the intensity o f the radiation. Thus E instein’s proposal v e ry nicely explains the ob ­
served dependence o f the photoelectric effect on the frequency o f the radiation.

Vo
TClectric field

F ig. 1-7. Experimental arrangement F ig. 1-8. Relation between stopping po­
for observing the photoelectric effect. tential and frequency of radiation in the
photoelectric effect.

W e can measure the m axim um kinetic energy E kitneix using the m ethod indicated
in F ig. 1-7. B y ap p lyin g a potential difference F betw een plates A and C, w e can
retard the m otion o f the photoelectrons. A t a particular vo lta ge F 0 the current,
indicated b y th e electrom eter E , drops suddenly to zero, which means th at no elec­
trons, not even the fastest ones, are reaching plate C. T h e n E k,maJC = e V 0 and
E q . (1.15) becomes

eV o = hv — φ0. (1.16)

B y changing the frequency v, w e can obtain a series o f values for the stopping poten­
tial F 0. I f E q . (1.16) is correct, the result o f p lottin g the values o f F 0 against v
should be a straigh t line. T h is is exactly w h at is obtained, as shown in F ig. 1-8.
I'l The foundations of quantum physics (1.5

T h e slope o f the straight, line is tan a = h/e. M easuring a, and using th e known
value o f e, w e m ay recalculate P la n ck ’s constant h. T h e result is th e same as that
found for b lack bod y radiation. T h is agreem ent can be considered as a further
ju stification o f P lan ck ’s assumption in vo lved in E q . (l.G ). /
F rom the observed valu e o f v0, one m ay also obtain the work function o f the
m etal, φη = Iivn, and com pare it w ith the value o f the w ork function obtained by
oth er means. T h e results are consistent.

1.5 Sva itvrin u o f U a d ia tion b y F r v v Flvvirontt

So far w e have considered on ly the energy associated w ith elect rom agnetic radiation.
H ow ever, an electrom agnetic w a ve carries momentum in ad d ition to energy. (T h is
is n ot surprising, since energy and m om entum are closely related.) N o tin g that
electrom agnetic radiation propagates w ith a v e lo c ity c, w e can show, using M a x ­
w e ll’s equations, that the relation between energy and momentum fo r a plane
electrom agnetic w a v e is

Ii = cp. (1.17)

B u t according to the th eory o f r e la tiv ity (see E q . A . 11), the energy o f a particle
o f rest mass m 0 and m om entum p is

I i — c λ / m lc 2 p 2. (1.18)

T h is becomes ident ical to E q . (1.17) when m 0 = 0. H ence w e m ay conclude that

the relation between energy and m om entum is the same for a plane electrom agnetic
w ave as for a particle o f zero rest mass.
W hen an electrom agnetic w ave is em itted, absorbed, or scattered, both energy
and m om entum are exchanged w ith the particles responsible for the process. T h e re ­
fore when w e an alyze an y process in which electrom agnetic radiation interacts w ith
charged particles w e must ap p ly the laws o f conservation o f energy and m om entum ,
being careful to take E q. (1.17) in to account for the part corresponding to the
electrom agnetic wave.
T h is result poses certain problem s when w e consider the interaction o f an electro­
m agnetic w a v e w ith a free charged particle, such as a free electron. If, for exam ple,
an electron absorbs an energy E from an electrom agnetic wave, it must also absorb
a m om entum p = E/c. N o w if we assume that the free electron was o rigin ally a t
rest in the observer’s fram e o f reference, the absorbed energy becomes the kinetic
energy o f the electron. But the kinetic energy o f an electron is related to its m om en­
tum /I0 by

Ek = c \ ^ m fc2 + p i — m cc 2,

and this relation is incom patible w ith />,. = E / c anil Iik = E , as required b y the
principles o f conservation o f energy and o f m omentum. T h u s w e m igh t conclude
that a free electron cannot interact w ith an electrom agnetic w a ve w ith ou t vio la tin g
the principles o f conservation o f m om entum or o f energy. T h e student m ay then
w onder w hy, when we w ere discussing the photoelectric effect in the preceding sec­
m Scattering of radiation by free electrons 15

tion, w e did not. m ention this problem at all. T h e reason is that, in the case o f an
electron bound to either an atom , a molecule, or a solid, the energy and mom entum
absorbed are shared both by the electron and the atom , the m olecule, or the solid
lattice to which the electron is coupled. In such circumstances it is alw ays possible
to split both en ergy and m om entum in the correct proportion so that both quanti­
ties are conserved. H ow ever, the atom,
molecule, or solid — each o f which has a
much larger mass than the electron—
\
carries (along w ith some m om entum ) U- Inci dent
only a small fraction o f the energy
available, so small that it is usually not
0 = 0° J I radi ation

considered at all. In the case o f a free

\ I I I I I *-
elect ron, since there is no oth er particle
with which the electron shares the
energy and the m om entum , no absorp­ I \

tion or scattering should be possible I \

I \
without viola tin g the conservation of 0 = 45° I I \
I
I
\
\
either o f the tw o quantities. I \

/ 1 \
V / I \

0 = 90°
\
/ \V S
/
/ I
I
I
I
\
\\
\

I I ! I I sV I *

/ I \
/ 1 \
/ 1 \
0=135° / 1 \
F ig. 1-9. Intensity distribution of the v / 1 X
radiation scattered by a free electron at I *
different scattering angles. I I I l! I _

E xperim ent, however, tells a d ifferent story. W h en w e an alyze the electrom ag­
netic radiation that has passed through a region in which free electrons are present,
we observe that, in ad dition to the incident radiation, there is another radiation
present, o f different frequency. T h is new radiation is interpreted as the radiation
scattered by the free electrons. T h e frequency o f the scattered radiation is smaller
than the frequency o f the incident radiation, and accordingly the w avelen gth o f
the scattered radiation is longer than the w avelen gth o f the incident radiation.
T h e w avelen gth o f th e scattered radiation depends on th e direction o f scattering
(F ig . 1 -9). T h is interesting phenomenon is called the Com pton effect, a fter the
Am erican physicist A . H . C om pton (1892-1962), w h o first observed and an alyzed
it in the early 1920’s.
G iv e n that λ is the w avelen gth o f th e incident radiation and X' that o f the scat­
tered radiation, C om pton found th at λ ' — λ is determ ined solely by the direction
of the scattering. T h a t is, if Θ is th e angle betw een the incident w aves and the
16 The foundations of quantum physics C1.5

d irection in which the scattered w aves are Detector

ob served (F ig . 1-10), the w a velen g th o f
th e scattered radiation λ ' is determ ined
in term s o f the scattering angle Θ b y the
experim ental relation

X' — λ = Xc ( l cos Θ),

(1.19)

w h ere Xe is a constant, w hose valu e is

tering.
Xc = 2.4262 X IO -12 m.

I t is called the C om pton wavelength fo r electrons: R e m em b erin g th a t λ = c/v,

w h ere v is the frequ ency o f the w ave, w e m ay w rite E q. (1.19) in the form

COS Θ). ( 1.20)

N o w the scattering o f an electrom agnetic w a v e b y an electron m ay be visualized

as a “ collision ” betw een the w a v e and the electron, since it comprises an exchange
o f en ergy and m om entum . A n d since the w a v e p ropagates w ith the v e lo c ity c and
its en ergy-m om en tu m relationship E = cp is sim ilar to th at for a p article o f zero
rest mass, this scattering m ust resem ble a collision in which one o f the particles has
zero rest mass and is m o v in g w ith v e lo c ity c.
T h is collision can be an alyzed v e r y sim ply. L e t us call E and E ' the energy and
m om entum o f the p article o f zero rest mass b efore and a fte r the collision; let
p = E / c and p ' = E '/ c be the corresponding values o f th e m om entum . G iv e n
th a t P q is the m om entum o f the electron a fte r the collision, th e principles o f con­
servation o f energy and m om entum y ield

P = P t+ Po, ( 1.21 )

E + TOcC2 = E ' + c y / m fc 2 + p 2· (1 .2 2 )

F ro m E q. (1.21) w e g e t p c = p — p ' . Squaring, w e obtain

pl = P 2 + P '2 ~ 2
p
·

wh ere Θ is the angle through w hich the p article o f zero rest mass has been d evia ted
or scattered. S olving E q. (1.22) for p i g ives us

_ (E + m ec - E f) 2 2 2
m ec
Ve 2

= ~ [ E 2+ E ' 2 + 2 -( E ') m ec2 -

E 2
1.5) Scattering of radiation by free electrons 17

Equating the two results for pi and canceling some common terms, we obtain
EE'
E - Er = (I - cos Θ).
m ec 2

Dividing both sides b y E E ' yields

(1.23)

T h e sim ilarity betw een Eqs. (1.20) and (1.23) is striking; it goes beyond a m ere
algebraic sim ilarity. B o th equations ap p ly to a collision process in its m ost general
sense. Also, as w e m entioned before, the energy-m om en tum relationship E = cp
for an electrom agnetic w a ve is similar to th at for a particle o f zero rest mass, to
which E q. (1.23) applies. T h e obvious conclusion is to link the frequency v and
the energy E b y w ritin g

E = hv, (1.24)

with a sim ilar expression for E '; th at is, E f = hv'. H ere h is a universal constant
which describes the p rop ortion ality betw een the frequency o f an electrom agnetic
wave and the energy associated w ith it in the "collision ” process. T h en E q. (1.23)
becomes

or
(1.25)

which is, in form , identical to E q. (1.20). T o obtain the equivalent o f E q. (1.19),

we m u ltip ly E q. (1.25) b y c and use X = c/v. T h e result is

λ' — X = (h/m ec ) ( I — cos 0). (1.26)

T h en the C om pton w avelen gth for an electron, Xe, is related to the mass o f the
scattering electron b y

Xe = h/mec. (1.27)

From the known values of Xe, w e, and c w e m ay com pute the value o f the constant
h, obtaining the same value th at w e found before for P lan ck ’ s constant in connec-
tion w ith blackbody radiation and the photoelectric effect. Thus E q. (1.24) is
essentially identical to E q. (1.6).
W e m ay then conclude th at w e can "e x p la in ” the scattering o f electrom agnetic
radiation b y a free electron if w e id e n tify the process w ith the collision o f a free
electron and a particle o f zero rest mass which has an energy E = hv before th e
collision and an energy E ' = hv' after the collision.
IS The foundations of quantum physics ( 1.6

I . Ii I tIioIonn
O ur explanation o f th e C om pton effect m ust be carefully an alyzed because o f its
possible far-reaching consequences. First let us restate our assumptions:
(a ) T h e scattering o f electrom agnetic radiation b y a free electron m a y be c o n -'
sidered as a collision between the electron and a particle o f zero rest mass.
(b ) E lectrom agnetic radiation plays the role o f the particle o f zero rest mass,
which for b re v ity w e shall call a photon.
(c ) T h e energy and m om entum o f the particle o f zero rest mass (o r the p h oton )
are related to the frequency and w avelength o f the electrom agnetic radiation by

E = Iiv, p=h/\. (1.28)

T h e second relation is due to the fact th at p = E / c = liv/c and v/c = l /λ. W e

m ay visualize the C om pton effect as the collision illustrated in Fig. 1-11. H e re a
photon o f frequency v collides with an electron a t rest, transfering to it certain
en ergy and m om entum . A s a result o f the interaction, the scattered photon has
a sm aller energy, and a correspondingly sm aller frequency ν'. T h e electron, a fter
the scattering, has a m om entum equal to the difference between the m om entum
o f the incident photon and that o f the scattered photon. W e can v e rify this fact
exp erim entally. It is a difficult experim ent, but it has been perform ed and the
results check v e ry well with theory.
I i '= he'

E = hv
h

Fig. 1-11. Momentum and energy Incident

relations in Compton scattering. photon

E lectron a fte r
sca tterin g

W h at is the physical m eaning o f the photon concept and o f the defining rela­
tions (1.28)? It is not a necessary conclusion th at electrom agnetic radiation is a
stream o f photons, which could be a possible pictorial explanation. R e fe rrin g to
'the"C om pton effect, w e m ay in terpret the photon energy E - Iiv and m om entum
p = Λ/λ as the energy and m om entum absorbed by the free electron from th e inci­
d ent electrom agnetic w ave. T h e photon o f energy E 1 = Iiv1 and m om entum
p' = Λ/λ' is then the energy and m om entum re-em itted b y th e electron in to th e
scattered radiation. In other words, w e m ay consider that the C om pton effect
OCCiu-S in tw o steps: first a photon o f energy hv is absorbed b y the electron, and
a fterw ard the electron em its a photon o f energy h v'. T h e electron acquires a kinetic
en ergy Ei1 = E - E ' and a mom entum p . . = p — p ' . which are related by

Ek = c V WIqC2 + P c ~ WI0C2,

as required b y the conservation o f energy and m omentum.

 Pholotis 19

On the basis o f this interpretation o f the C om pton effect, togeth er w ith our p re­
vious discussion o f Iilackbody radiation and the photoelectric effect, w e m ay con­
clude that a photon is the “ quantum ” o f electrom agnetic energy and m om entum
emitted or absorbed in a single process by a charged particle. I t is entirely deter­
mined b y the frctpicncy o f the radiation. T h erefore, we m ay state the follow ing
principle:

When an electromagnetic wave interacts with a charged particle, the

amounts o f energy and momentum which are exchanged in the process
are those corresponding to a photon.
,, ,J

T h e principle stated a b o v e is one o f the fundam ental laws o f physics. It is ap p li­

cable to all radiative processes in v o lvin g charged particles and electrom agnetic
fields. I t does not stem from an y law that w e have stated or discussed previously,
but is a com pletely new principle, to be considered on the same level as such uni­
versal laws as the conservation o f energy and momentum. T h e discovery o f this
law in the first quarter o f this century was a m ilestone in the developm en t o f
physics.
T h e concept o f the photon suggests a sim ple pictorial representation o f the
electrom agnetic interaction between tw o charged particles, as shown in F ig. 1-12.

A ft e r p I

In teraction

F ig. 1-12. Electromagnetic interac­

tion considered as an exchange of pho­
tons. The photons transfer energy and
momentum from one charge to the
other.

T h e interaction corresponds to an exchange o f momentum and energy. T h e initial

m om enta /J1 and /J2 o f the particles becom e p\ and p 2 a fte r the interaction. A l ­
though the interaction is not localized a t a particular instant, for sim p licity w e
have indicated it a t a particular time, and a t positions A and B . P a rtic le I inter­
acts w ith particle 2 v ia its electrom agnetic field, w ith the result th at particle 2
takes a certain am ount o f energy and m om entum from the field, equivalent to a
photon, w ith a corresponding change in its m otion. T h e m otion o f particle I must
then be adjusted to correspond to the new field, which is the original field minus
one photon. O f course, the reverse process is also possible, and particle I m ay
absorb a photon front the field o f p article 2. W e m ay say then that what has hap­
pened is that, between particles I and 2 , there has been an exchange o f photons.
In other words,

electromagnetic interactions can be pictured as being the result o f the

exchange o f photons between interacting charged particles.
20 The foundations o f quantum physics (1.6

Frequ ency, N am e of P h oto n Wavelength,

Hz r a d ia t io n e n e rg y , e V ni

IO22-
IO7 -1 0 ' 3 — I X -u n it, X U
IO2' - Ga
IO- ' 2
10“ 10»
IO5 - 10- "
10‘9
_X-rays_ IO4 — J O - i o — I angstrom , A
10'»
l·- IO3 10-» — I nanom eter, n m
IO l i
IO2 - 10-*
10 "> U lt r a v io le t
10 IO- 7
IO ' 3
- I O " 9 — I m icron, μ
I
IOm V is ib le
- 10-' ΙΟ- 5
IO '3 - Infrared
- IO- 2 IO"4
IO '2 -
IO-3 ΙΟ " 3
10 " -

M ic rw a v e IO' 4 - I O - 2 — I cen tim eter, cm

10'0 -
IO' 5 10-'
IO9
10-» 10° — I m eter, m
10»
I-IO " 7 - 10'
10"
I M H z -IO 9
10- » -IO 2

IO- 9 - I O 3 — I kilom eter, km

IO5
H a d i o fr e q u e n c y - 10-"> -IO 4
10»
- 10- " -IO3
I k H z — IO3

F ig. 1-13. T h e electrom agnetic spectrum.

A t an y instant, the total m o m e n tu m o f a s y s te m o f tw o charged particles is

P I + P t + Pficldi

w here p r,iW is the m om entum a s s o c ia te d w ith the electro m ag n etic field o f th e

charged particles and the to ta l e n e r g y is E 1 + E 2 + E M i i.
F igu re 1-13 shows the v a rio u s re g io n s o f t h e ele ctro m a g n e tic spectrum, w ith th e
com m on names given to each re g io n . T h e w a v e le n g th , frequ ency, and energy o f
the associated photons are also g iv e n .

E X A M P L E 1.5. Express the en ergy of a p h oton in electron volts in terms of its w ave­
length given in meters. Use the result to o b ta in the wavelength of x-rays in terms of the
accelerating voltage applied to an x-ray tube.

S o lu tio n : From E — hv and \v — c, we have th at E = hc/\. But

he = (6.6256 X IO-3 4 J s) (2.9979 X 108 m s - 1) = 1.9863 X IO- 2s J m .

Remembering that I e V = 1.6021 X IO- 10J, we see that he = 1.2397 X 10- e eV m.

 Photons 21

Wavelength λ, A

Fig. I —I t. Intensity distribution in the x-ray spectrum of molybdenum as a function

of the applied voltage. The K - scries excitation potential is 20.1 kV and appears as the
characteristic spikes on the 25-kV curve.

TheVefore
E = 1.2397 X IO -6A « 1.24 X IO -6A ,

where E is expressed in electron volts and X in meters.

As we explained in connection with Fig. 1-3, x-rays are produced by the impact of fast
electrons against the anode material of an x-ray tube. The energy of an electron may be
radiated as a result of successive collisions, so that several photons are produced; or it
may all be radiated as a single photon in just one collision. Obviously the most energetic
photons coming out of the x-ray tube would be those emitted by means of the latter
process, and these photons have the shortest wavelength. In other words, given that V
is the accelerating voltage (in volts), which is also the same as the energy of the electrons
(in eV ), the wavelengths of the x-rays produced are equal to or longer than the threshold
wavelength, satisfying the relation

1.24 X IO- 6
Xo = γ m.

For example, in a television tube, electrons are accelerated by a potential difference of

the order of 18,000 V. When the electrons reach the screen of the tube, they are abruptly
stopped. Thus a television screen emits x-rays for the same reason as an x-ray tube does.
(The intensity, however, is quite low.) The minimum wavelength of the x-rays produced
when the electrons are stopped at the screen is X = 6.9 X IO-11 m. The above relation
has been ,confirmed experimentally. Figure 1-14 shows the intensity of x-rays from an x-
ray tube as a function of the wavelength of the emitted photons for different values of V .
22 The foundations of quantum physics (1,7

1.7 Stationarμ Statos

W h en an electrom agnetic w a v e interacts w ith a system o f charges, such as an
atom , a molecule, or a nucleus, th e electric and m agnetic fields o f the w a v e disturb
the m otion o f the charges, In the language o f classical physics, w e could say th at
the w ave impresses a forced oscillation on the natural m otion o f the charges. T h is
results in absorption o f energy b y the system o f charges. A classical oscillator
responds most easily when the frequency o f the forced oscillations is the same as
its natural frequency, a situation which is called resonance. W h en there is reso­
nance, the rate a t which the oscillator absorbs energy is maximum.
I t has been found experim entally th a t atoms, molecules, nuclei— in general, any
assem bly o f charged particles— have a series o f resonating frequencies iq , v2, V3 , . . .
a t which the absorption o f electrom agnetic radiation is appreciable. A t all other
frequencies the absorption is negligible. T h e resonating frequencies V1, v2, v3, . . .
constitute the absorption spectrum o f the substance. L e t us assume that the system
in itially has a m ost stable state o f m inim um energy, called the (/round state. Then,
when the system absorbs electrom agnetic radiation, it passes to an oth er state o f
higher energy, called an excited state. In the case o f a classical oscillatin g electric
dipole, an excited state w ould correspond to a larger am plitude o f oscillation.
O bviously a system o f charges in an excited state m ay release its excess energy
in the form o f electrom agnetic radiation. T h e frequencies observed in the radiation
em itted constitute the emission spectrum o f the system o f charges. E xperience has
shown that

the frequencies observed in the absorption spectrum o f a system of

charges are also observed in the emission spectrum o f the system.

F o r example, sodium atom s show preferential absorption for ligh t o f frequency

equal to 5.09 X IO u H z or w avelength equal to 5.89 X IO- 7 m. T hese are pre­
cisely the values o f the frequency and w avelength o f the yello w lig h t em itted by
incandescent sodium vapor.
T h e existence o f a spectrum composed o f well-defined frequencies was a problem
th a t puzzled physicists a t the end o f the last century and the beginning o f this one.
T o solve this problem , a new and revolu tion ary idea was advanced in 1913 by the
Danish physicist N iels B ohr (1885-1962). B ohr used the photon concept as ana­
lyzed in the previous section and extended P lan ck ’s assum ption as expressed b y
E q . (1.6). Suppose that an atom in a state o f energy E absorbs radiation o f fre­
quency v and thus passes to another state o f higher energy E '. T h e change in energy
o f the atom is E ' — E . On the other hand, the en ergy absorbed from the radiation
in a single process must be th at o f a photon hv. C onservation o f energy requires
th at both quantities be equal. T h erefore

E' - E = hv, (1.29)

an expression called B oh r’s form ula. Sim ilarly, if the atom passes from a state o f
energy E ' to another state o f low er energy, E , the frequency o f the em itted radia­
tion must be given b y E q. (1.29).
 Slalioimrv stales 23

T h e fact th a t only certain frequencies iq, v2, v3, . . . are observed in emission
and ab sorption can be explained if we assume th at the energy o f the atom can have
only certain valu es E ,, E 2, E 3, . . . Each allow ed energy value is called an energy
level. T h e n th e on ly possible frequencies which result in emission or absorption o f
radiation are th ose corresponding to transitions between tw o allow ed energy levels;
that is, v = ( E , — E j)/ h . Thus B ohr’s assumption m ay be stated as follow s:

T h e energy o f a system o f charges— either a/ι atom, a molecule, or a

nucleus— can have only certain values E 1, E 2, E 3, . . .; that is, the
energy is quantized. The stales corresponding to these energies are
called stationary states and the possible values o f the energy are called
energy levels.

Absorption o f electrom agnetic radiation, or o f any other energy, results in a tran­

sition o f the a to m (o r m olecule or nucleus) from one stationary state to another o f
higher e n e rgy ; emission o f electrom agnetic radiation results in th e reverse process.
T h e frequ en cy o f the radiation in vo lved in the process is given b y Eq. (1.29).

Fig. 1-15. T ransitions between

stationary states. T h e relative spac­
ing of the energy levels and the pos­
sible transitions depend on the nature
of the system.

(a ) A bsorption (I)) Emission

Some transitions are show n schem atically in F ig. 1-15. Λ process in which an atom
in its ground state, represented b y A , absorbs a photon and passes to an excited
state, represented b y A *, is designated b y

A + hv A *.

T h e reverse process, photon emission, can be expressed by

A * ->· A + hv.

T h e idea o f system s o f charges h a vin g on ly a discrete set o f stationary states is

com pletely foreign to new tonian mechanics. B y the laws o f newtonian mechanics,
the m otion o f a p a rtic le is determ ined by the initial conditions o f the particle,
which are considered arb itra ry . T h u s a p article m ay have an y energy, determ ined
by the a rb itra rily chosen initial conditions (position and v e lo c ity ). T h is applies,
2'i The foundations of quantum physics (1.7

for exam ple, when an artificial satellite is placed in a stable orbit. A n astronaut
m a y arb itra rily change the orbit, and thus also the energy, o f his spaceship sim p ly
b y changing the v e lo c ity a t a particular time. B y th e same token, new tonian
m echanics allows the electron in a hydrogen atom to have any arb itra ry energy,
depending on the kinem atical conditions th a t exist when the electron is captured
b y the proton to form the atom , and the electron could change its o rb it b y absorb­
ing an arb itrary am ount o f energy. N atu re, however, appeals to w ork d ifferen tly:
on ly certain m otions are allowed, or possible. In other words, the existence o f
s tation ary states must be accepted as a fundam ental fa ct o f nature.
T h e acceptance o f the idea o f stationary states poses another d ifficu lty within
the fram ew ork o f classical physics. W h en an electron revolves around a nucleus
in an atom , its m otion has both tangential and centripetal acceleration; i.e., its
m otion is accelerated. T h erefo re one w ould think th a t the electron w ould be
radiating energy continuously. A s a result, the electron’s energy would be decreas­
in g continuously and its o rb it w ould be shrinking. T h is w ould m ake the existence
o f stationary states impossible. H ow ever, neither this contraction o f m a tter nor
th e continuous radiation o f energy associated w ith it h a ve been observed. T h e re ­
fore, since the predictions o f classical electrodynam ics are not follow ed, w e m ay
conclude th at an electron (o r a charged particle) m ovin g in a stationary state is
g overn ed b y some addition al principles w hich w e have n ot y e t considered. We
shall explore these new principles in C hapter 2.
B o h r’s assumption o f stationary states was m ade on an ad, hoc basis, w ith ou t
an y firm theoretical justification. T h e success o f his hypothesis, however, prom pted
oth er physicists to perform experim ents to test the idea. Q uickly there accum ulated
a great w ealth o f inform ation, from which new and unsuspected atom ic properties
w ere discovered. T h is same situation has occurred several other tim es in contem ­
porary physics. A physicist, w ith great intuition and courage, proposes a new and
bold con cept; the idea provokes new thinking and experim ents, and soon new and
unsuspected vistas are opened.
T h e stationary states do not necessarily constitute a discrete energy spectrum.
In m any instances all values o f the energy in a certain energy range (o r band) are
allow ed and a continuous energy spectrum results. L e t us consider, for example,
the case o f an electron and a proton, and take the zero o f energy when both the
electron and proton are a t rest and are separated by a v e ry large distance. T h en
all stationary states o f n egative energy, which correspond to bound states in
which the electron m oves around the proton to form a hydrogen atom , arc quan­
tized and the energy o f such states can have on ly certain values Ε κ , E p , E m , . . .
(F ig . 1-10). On the oth er hand, the states o f positive energy are not quantized,
and their energy m ay have any value. T h ese states are unbound and correspond
to the situation in which an electron is thrown, from a v e ry large distance and w ith
a certain initial kinetic energy, against a proton; the electron, a fte r passing near the
proton, is deflected from its original direction o f m otion and recedes to an infinite
separation w ith out the form ation o f a bound system. T h e energy o f the system
in this case is determ ined b y the initial kinetic energy o f the electron, which m ay
be a rb itra rily chosen.
Ί .7 ) Slalionary slates 25

Transitions m a y occur betw een tw o states o f the discrete energy spectrum, such
as ab and cd in Fig. 1-10, or between a state o f the discrete spectrum and a state
of the continuous spectrum, such as e/, or between tw o states o f the continuous
spectrum, such as gh.

E=O

Fig. 1-16. Origin of the discrete

and continuous energy spectrum
due to discrete stationary states.

E X A M P L E 1.6. Energy and momentum conservation in radiative transitions.

S o lu tio n : A t first sight Eq. (1.29) is correct insofar as energy conservation is concerned.
However, a closer examination indicates that it requires a slight modification. In Sec­
tion 1.6 we noted that a photon carries a momentum Λ/λ = hv/c in addition to the energy
hv, and that both momentum and energy must be conserved in radiative transitions from
one state to another. Let us first consider emission by an atom at rest. Initially, before
the transition, its momentum is zero. After the transition the atom must recoil with a mo­
mentum equal and opposite to the momentum of the photon; that is, 0 = p„tom + Pptioton
or, in magnitude,

Pntom — Pphoton llv/c. (1.30)

How let us consider energy conservation. Initially we have an atom at rest in a stationary
state of energy E i and after the transition an atom in a stationary state of energy E/
with kinetic energy pi;tom/2.1/ and a photon of energy Iiv. Therefore energy conservation
requires that
2
P atom
E i = Z?/ + hv (1.31)
W

or, using Eq. (1.30),

Ei E/ hv ( l + 2 ] [ c2^ (1.32)

When hv is very small compared with 2.1/c2, the last term is negligible and Eq. (1.32)
reduces to Eq. (1.29). This is the case for atomic and molecular transitions. In general,
26 The JoundaHons o f quantum physics ( 1.8

hv is smaller than M c 2, and we may write Eq. (1.32) in the form

- <E ·· - * '> ( ' + 237 ? Γ - <*■ - E '> ( ' -

where we have used the expansion (I -|-x) -1 = I — x - ) - · · · , with x = hv/2Mc2, a

quantity small compared with unity. In the last term we can replace Iiv by /?,· — Ej,
resulting in

hv = E i - E t - , ( 1.33)

where the last term is essentially the recoil energy of the atom. Therefore, in the emission
process, the energy of the emitted photon is slightly less than the difference between the
two energy levels of the emitter (atom, molecule, or nucleus). The difference is the re­
coil energy of the emitter.
On the other hand, for the absorption process we must m odify Eq. (1.31) by writing

E i + hv = (1.34)

since there is now a photon in the initial state but not in the final state. Conservation of
momentum requires that />„,<>,„ = Pphoton, which again is equivalent to Eq. (1.30). So,
when we use the same approximation as above, Eq. (1.34) becomes

- I B, - B,) ( ) - 5 ^ ) " ‘ - (ft - ft) ( l + ^ i)

or
2
hv = E j — E i + ^ ^ c2 1 ■· (1.35)

Therefore, for absorption to take place, the energy of the absorbed photon must be slightly
greater than the energy difference between the two levels of the absorber to account for
the kinetic energy of the recoiling absorber.
A consequence of this analysis is that a photon emitted by a system (atom, molecule,
or nucleus) in the transition a —> 6 cannot be absorbed by another identical system in
order to undergo the reverse transition b —> a, and therefore the emission spectrum is not
identical to the absorption spectrum. W e shall come to this matter again in Example 1.10.
For atomic and molecular transitions in which E j — E i is of the order of few electron volts
and M c 2 is of the order of 1 0 " eV, the correction term in Eqs. (1.33) and (1.35) is about
IO-10 eV and thus is negligible. On the other hand, for nuclear transitions, E j — Ei may
be of the order of IOfi eV. Since M c 2 is of the same order as in atomic transitions, the cor­
rective term is about 10 eV, which is relatively more important.

I . it K xpvrinivnta l K riilvn vv o f S tationa ry Statvn

So far w e h a ve introduced the idea o f station ary states as a convenient concept to
explain the discrete spectrum o f atom ic systems. H ow ever, the existence o f transi­
tions betw een stationary states is am p ly corroborated by m any experim ents. The
m ost characteristic is th at o f inelastic collisions, in which p art o f the kinetic energy
 Experimental evidence of stationary stales 27

of the p rojectile is transferred as internal energy to the target. T h ese are called
inelastic collisions o f the first kind. Inelastic collisions o f the second kind correspond
to the reverse process.
Suppose th at a fast particle q collides w ith an oth er system A (w hich m ay be an
atom, molecule, or nucleus) in its ground state o f energy E i . A s a result o f the
projectile-system interaction (w hich m ay be electrom agnetic or nuclear), th ere is
an exchange o f energy. L e t E 2 be the energy o f the iim t excited state o f the system .
The collision w ill be elastic (i.e., the kinetic en ergy w ill be conserved) unless the
projectile has enough kinetic energy to transfer the excitation energy E 2 - E i to
the target. W h en this happens the collision is inelastic, and w e m ay express it by

A }~ t/fast * E T 9»low

W lien the mass o f the p rojectile q.is v e ry sm all com pared w ith th at o f the target A ,
as happens fo r the case o f an electron colliding w ith an atom , the con dition for in­
elastic collision (see E xam p le 1.7) is

Ek > E2 - E 1, (1.36)

where E k = \mv2 is the kinetic energy o f the p rojectile before the collision. T h e
kinetic energy o f the p ro jectile a fte r the collision is then E 1
k = E k — ( E 2 — E i ),
since the energy lost b y the p rojectile in the collision is E 2 — E i .
T o g iv e a concrete exam ple, suppose th at an electron o f kinetic energy E k m oves
through a substance, let us say mercury vapor. P rovided th at E k is sm aller than
the first excitation energy o f m ercury, E 2 - E it the collisions are all elastic and
the electron m oves through the vapor, losing en ergy v e ry slow ly, since the m axi­
mum kinetic energy lost in each collision (see P ro b lem 1.55) is ap p roxim ately

AEk « — 4 (m . J M )E k ~ 5 X IO- 0J?*.

How ever, i f E k is larger than E 2 - E it the collision m ay be inelastic and the elec­
tron m ay lose the energy E 2 — E i in a single encounter. I f the initial kinetic
energy o f the electron was not much larger than E 2 - E it the energy o f the elec­
tron a fter the inelastic collision is insufficient to excite other atom s. T h e rea fter
the successive collisions o f the electron w ill be elastic. But if the k inetic energy o f
the electron was in itia lly v e r y large, it m ay still suffer a few m ore inelastic colli­
sions, losing the energy E 2 — E i a t each collision and producing m ore excited
atoms b efore being slowed down below the threshold fo r inelastic collisions.
T h is process was observed for the first tim e in 1914 b y Franck and H ertz. T h e ir
experim ental arrangem ent is indicated schem atically in Fig. 1-17. A heated fila­
m ent F em its electrons which arc accelerated tow ard the grid (7 b y a variab le
potential V . T h e space between F and G is filled w ith m ercury vapor. B etw een the
grid G and the collecting plate P a small retard in g potential F ', o f ap p roxim ately
0.5 vo lt, is applied so th a t those electrons which are left w ith v e ry little kinetic
energy a fte r one or m ore inelastic collisions cannot reach the plate and are not
registered b y the galvanom eter. A s V is increased, the plate current I fluctuates
28 The foundations of quantum physics

+ -

F ig. 1-17. Franck and Hertz experimental Fig. 1-18. Electron current versus ac­
arrangement for analyzing inelastic collisions celerating potential in the Franck-Hertz
of the second kind. experiment.

as shown in F ig. 1-18, th e peaks occurring a t a spacing o f abou t 4.9 volts. T h e

first dip corresponds to electrons th at lose all th eir kinetic energy a fte r one inelastic
collision w ith a m ercury atom , which is then le ft in an excited state. T h e second
d ip corresponds to those electrons th at suffered tw o inelastic collisions w ith tw o
m ercury atoms, losing all th eir kinetic energy, and so on. T h e excited m ercury
atom s return to their ground state b y emission o f a photon, according to H g * —>
H g -)- hv w ith hv = E q — E 1. F rom spectroscopic evidence w e know th at m ercury
vap or, when excited, em its radiation whose w avelen gth is 2.536 X IO- 7 m (o r
2536 A ), corresponding to a photon o f energy hv equal to 4.86 eV. R a d ia tio n o f
this w avelength is observed com ing from the m ercury v a p or during the passage o f
the electron beam through the vapor. T h u s this sim ple experim ent is one o f the
m ost striking proofs o f the existence o f stationary states.
A n oth er sim ilar experim ent is the coulomb excitation o f nuclei. F o r exam ple,
w hen a proton passes near a nucleus, the electrical interaction betw een the tw o
m ay g iv e rise to an inelastic collision, resulting in the excitation o f the nucleus to
one o f the lowest excited states. T h e nucleus returns to its ground state, em ittin g
ganuna-ray photons which have an energy o f the order o f several keV. F o r that
reason coulom b excitation is one o f the m ost im portant experim ental m ethods for
d etectin g and an alyzin g the low -lyin g stationary states o f nuclei.

E X A M I’ L E 1.7. Calculation of the threshold kinetic energy required for the excitation
of the target in an inelastic collision of the first kind.

S o lu tio n : Let us designate the mass of the projectile and the target by m and M , respec­
tively. W e assume that the target is initially at rest in the laboratory or /.-frame of
reference. Given that p is the momentum of the projectile before the collision and p '
and I’ the momenta of projectile and target after the collision, the conservation of mo­
mentum requires that

p = p I’ (1.37)
 \

j Interaction of radiation with matter 29

Similarly, if £ i is the energy of the initial stationary state of the target and £'2 the energy
of the final state, the conservation of energy requires that

I 2 I p I /2 , I j\2 I JI

2- P + * 1- 2 + 2MP + E i

or, if wc set A E = £2 — E i , then

^ / = ^ ' 2+ ύ ϊρ2+ΕΕ· ( 1 ·3 8 )

The minimum kinetic energy of the projectile required for the process is that in which
both projectile and target are at rest in the center of mass or C-frame of reference after
the collision, so that all the kinetic energy in the C-frame is used in the excitation of the
target. In this case both target and projectile, after the collision, move in the C-frame
with the same velocity ccm of the center of mass of the system. Therefore p ' = mvcm
and P = M v c m - But if v is the velocity of the projectile before the collision, we have
that

ecu =
m+ M
And therefore

, m e mp mM v Mp
P = m" i+ M = '„
m~+f "Ir
M ’ P = m + M m+ M

equations which are, of course, compatible with Eq. (1.37). Substituting these values in
Eq. (1.38) after a straightforward simplification, we obtain

m+ M
M
( i p2) “
AE

& - ά " ’ - ( Ι + ϊ ) ΔΕ· ('·39>

This equation gives the threshold kinetic energy which the projectile must have for excit­
ing the target to its first excited level. I f the projectile is much lighter than the target,
m <5ζ M ; then we have Eu = A E = £2 — £ 1. This is the situation for an inelastic colli­
sion of an electron with an atom or molecule; we used this situation in our analysis of the
Franck-Hertz experiment. However, when nuclei undergo coulomb excitation because
of their inelastic collisions with protons, we must use Eq. (1.39). The reason for this is
that, in general, especially in collisions with light nuclei, m/M may not be small when
compared with unity.

1.9 Mntvrariion o f Mtadiation irith M a H o r

T h e interaction o f radiation w ith m atter is one o f the fundam ental processes respon­
sible for m any phenomena occurring in the universe. F or exam ple, the earth is sub­
je c t to a continuous flow o f electrom agnetic radiation from the sun, which makes
life on earth possible through the process o f photosynthesis (th a t is, the form ation
o f new' compounds, m ainly carbohydrates, ou t o f the synthesis o f carbon d ioxide
and w ater as a result o f th e absorption o f photons; a com pound called chlorophyll
30 The Jowidalions of quantum physics (1.9

p lays an im portant role in the rea ction ). T h e process can be w ritten as

GCO2 T O H 2O -j- Iihv —►C eH l 2O 0 OO2.

T h e num ber n o f photons in vo lved is not fixed; th eir energy falls m ostly in the
visib le region o f the spectrum. T h e process is much m ore com plicated than the
a b o v e equation would suggest and a c tiv e research 011 it is still goin g 011. P h o to ­
synthesis is im portant not on ly because it produces carbohydrates, which are the
u ltim ate source o f food (and thus o f en ergy) for m ost liv in g organisms, but also
because it controls the am ount o f oxygen in the atm osphere b y liberating oxygen,
which, 011 the other hand, is qu ick ly consumed in the m any ox id izin g processes
occurring 011 the earth.
P hotosynthesis is just one exam ple o f m any reactions initiated b y the absorption
o f radiation. T h e study o f such reactions is called photochemistry. Each ph oto­
chem ical reaction requires th e intervention o f photons o f a certain energy. A n oth er
exam ple o f processes due to absorption o f radiation is the dissociation o f a m ol­
ecule b y the absorption o f a photon. T h a t is,

A B - f hv —> A + B.

O ne such reaction, o f great geophysical and biological im portance, is the dissocia­

tion o f oxygen in the atm osphere b y the absorption o f ultraviolet radiation o f w a v e ­
length in th e range o f IGOO A to 2400 A (th a t is, photons w ith an energy between
7.8 e V and 5.2 e V ). W e m ay express this process b y the equation

0 2 + hv — O + 0 .

T h e atom ic oxgen produced com bines w ith m olecular oxygen to form ozone, O 3,
which in turn undergoes photochem ical dissociation by absorption o f u ltraviolet
radiation o f w avelength between 2400 A and 3G00 A (th at is, photons o f energy
between 5.2 e V and 3.4 e V ). T h e reaction is

0 3 + hv -> O - f O 2.

T h ese tw o reactions absorb ultraviolet radiation so strongly th at th ey rem ove prac­

tic a lly all the u ltraviolet radiation com ing from the sun b efore it reaches the
earth's surface. I f this u ltra violet radiation w ere able to reach the earth ’s surface,
it w ould d estroy m any organisms b y means o f photochem ical reactions w ith cell
com ponents, enzym es, etc.
T h e photographic process is still another exam ple o f a photochem ical reaction.
U n der the action o f radiation, molecules o f silv er brom ide undergo decom position,
w ith th e silver atom s form in g a so-called laten t im age 011 a sensitized film. I>ater,
in the developin g process, the film is treated in such a w ay that a perm anent im age
is formed.
W h en the photon has enough energy, its absorption b y an atom o r a m olecule
m ay result in the ejection o f an electron. W h a t is le ft is an ionized atom or m ol­
1.9) Interaction o} radiation with matter 31

ecule. W e m ay w rite the process as

A + hv - * A + + e .

T h is process, called photoionization, is the eq u iva len t o f the photoelectric effect in

m etals discussed in Section 1.3. F o r th at reason it is also called the atomic photo­
electric effect. A s a result o f photoionization, w h en a beam o f ultraviolet, x- or 7-
radiation passes through m atter, it produces ion ization along its path. L e t us
designate the energy required to extract an electron from an atom or m olecule b y
/; this energy is called the ionization potential. T hen the kinetic energy o f the
ejected electron is g ive n b y

Ek - hv — I , (1 .4 0 )

an equation analogous to E q. (1.14). (In this equation, incidentally, w e h ave

neglected the recoil energy o f the ion.) E q u a tio n (1.40) shows that, in order to
produce photoionization, the energy o f the photon must be equal to or larger than
I. T h e value o f I depends on the stationary sta te initially occupied b y the ejected
electrons. For exam ple, if an electron is to be ejected from the ground state in a
hydrogen atom , the m inimum energy o f the photon must be 13.6 eV. B u t if the
electron is in the first excited state, on ly 3.4 e V a re required. F o r helium atom s the
ionization energy needed to rem ove an electron from the ground state is 24.6 eV.
In the region o f the upper atm osphere called the ionosphere, the large concen­
tration o f ions and free electrons (abou t 10" per m 3) is due m ostly to the photo­
electric effect in atom s and molecules produced b y u ltraviolet and x-radiation from
the sun. Som e o f the reactions that occur m ore frequ en tly are

N O + hv -> N O + -F e ~ (5.3 e V ),
N 2 + Iiv - * N / + e_ (7.4 e V ),
O 2 -F hv —> O f + e ~ (5.1 e V ),
H e + hv —» H e + + c ~ (24.6 e V ).

T h e ionization potentials are indicated in parentheses. M a n y other secondary

reactions take place in the atm osphere as a result o f these ionizations.
A process which is the reverse o f p h otoion ization is radiative capture. In radia­
tiv e capture, a free electron w ith kinetic energy Ek is captured into a bound state
by an ion w ith the emission o f a photon. T h a t is,

A + -fe —* A -F hv.

T h e energy o f the photon is

Iiv = Ek + I. (1.41)

W h en the energy o f a photon is much larger than the binding energy o f the
electron in an atom or molecule, the electron can be considered as free. In th at
case C om pton scattering (Section 1.5) is a m ore probable process than the photo-
 ■

32 The Joundalions of quantum physics ( 1.9

K Absorption edge

K r2 10- * I 10 IO2
P h o to n en ergy, M e V

F ig. 1-19. Macroscopic cross sections for the absorption of photons in aluminum and
lead. T lie solid curves are the total cross sections. Those labeled I are the partial cross
sections due to the photoelectric effect; those labeled I I are partial cross sections due to
the Compton effect; those labeled I I I are partial cross sections due to pair production.

electric effect. I f the energy o f the photon is larger than 2mcc2 ( = 1-02 M e V , which
is tw ice th e rest energy o f the electron), y e t another process m ay occur: the crea­
tion o f an electron-positron pair. (T h e positron is a particle havin g the same mass
as the electron, but p ositive charge.) T h e creation o f an electron-positron pair,
called p a ir production, m ay be writ ten as

Iiv —> e + + e~. (1.42)

T h is process w ill be discussed in detail in Section 9.3. A t present, let us say on ly

that it consists in the transform ation o f a photon into an electron plus a positron.
Since the energy associated w ith the rest mass o f an electron o r a positron is mcc2,
the minimum energy o f the photon needed to produce an electron-positron pair
must obviou sly be 2m,.c2.
A t high energy, electrom agnetic radiation m ay also interact w ith atom ic nuclei,
either raising them to an excited state, ejectin g a nuclear particle (such as a proton )
in a so-called photonuclear reaction, or even breaking the nucleus apart. These
nuclear processes w ill be discussed in C h ap ter 8.
W hen a beam o f radiation passes through m atter, its energy is gradu ally absorbed
by the various processes we have m entioned. Thus, given th at I o is the inten sity
o f the radiation before it enters the substance, its intensity a fte r it has traversed a
1:10) Particles and fields 33

thickness x o f the substance is given b y

I = Io e ~ Sz, (1.43)

where S (expressed in m eters-1 if x is expressed in m eters) is a qu a n tity character­

istic o f each substance and o f each process; it is called the coefficient o f linear ab­
sorption or the macroscopic cross section. I t is a function o f the energy o f the photons
(fo r the d erivation o f E q. 1.43, see E xam ple 8 .8).
F o r each substance, there is one m acroscopic cross section for each possible
process, such as photoelectric effect, C om pton scattering, pair production, etc.
T h e to ta l cross section o f a substance is the sum o f all partial cross sections. F ig ­
ure 1-19 shows the individual and total m acroscopic cross sections for aluminum
and lead for the three processes m entioned. N o te that a t low energy the photo­
electric effect is the m ost im portant, a t m edium energies the C om pton effect
dom inates, and a t high energies pair production is the main process.

I. IO I tUrtivIes and Fields

A n oth er im portant revolution in physical concepts took place a t the end o f the
first quarter o f this century, and radically changed our approach to the description
o f m otion o f a particle.
Our sensory experience tells us th at the objects w e touch and see have a w ell-
defined shape and size and therefore are localized in space. W e thus tend to extrap­
olate and think o f the fundamental particles (i.e., electrons, protons, neutrons, etc.)
as havin g shape and size, and so w e tend to im agine them as being som ewhat like
small spheres, w ith a characteristic radius, as w ell as mass and charge. Th is, how­
ever, is an extrapolation beyond our direct sensory experience and w e must analyze
it carefully before w e accept it.
E xperim ents have shown that our extrapolated sensory picture o f the basic con­
stituents o f m atter is erroneous. T h e dynam ical beh avior o f elem entary particles
requires that we associate w ith each p article a field— a mailer field— in the same
w a y that, in th e reverse manner, we associate a photon (which is equivalent to a
particle) w ith an electrom agnetic field. T h is m atter field describes the dynam ical
condition o f a particle in the same sense th at the electrom agnetic field corresponds
to photons which h ave precise m om entum and energy. In discussing the connec­
tion betw een the m atter field and the dynam ical properties o f the particle (i.e.,
m om entum and en ergy), we m ay be guided b y the relations previously found for
the photon. W ritin g the relations (1.28) in reverse, w e m ay assume that the w a ve­
length λ and the frequency v o f the m onochrom atic field associated w ith a particle
o f m om entum p and energy E are given b y

where h, as before, is P la n ck ’s constant. These relations were first proposed in 1924

b y the French physicist Louis de B ro glie (1892- ), and for th at reason λ = h/p
is som etim es called the de B roglie wavelength o f a particle. Introducing the w ave
num ber k = 2ir/\ and the angular frequency ω = 2-κν, w e m ay w rite the rcla-
35 The Joundalions of quantum physics

tions (1.44) in the m ore sym m etric form

or, defining a new constant designated b y h and called h-bar,

h = h /'lir = 1.0.544 X IO-34 J s,

w e have
p = ΛAr, E - Ιιω. (1.4.5)

I f our assumption, as expressed b y Eqs. (1.44) or (1.4.5), is correct, w e m ay expect

th a t w h en ever the m otion o f a p article is disturbed in such a w a y th at the field
associated w ith it cannot propagate freely, interference and diffraction phenomena
should be observed, as is the case for elastic and electrom agnetic waves. T h is is
indeed what happens.

F ig. 1-20. Experimental arrangem

for observing electron diffraction throi
crystalline material.

B efo re w e discuss the experim ents that reveal interference and diffraction o f th e
m atter field, le t us try to estim ate the value o f the de B roglie w avelength λ asso­
ciated w ith a particle. Electrons accelerated b y an electric p oten tial V gain an
energy e V ; hence their kinetic energy is p /2mr = e V so that p = \/:2 )itL.eV.
T h erefore, introducing the values o f e, mc, and Λ, w e obtain the de B roglie w a ve­
length o f such electrons

λ = h / V 2 m ec V = 1.23 X IO- V v I 7 m, (1.40)

where V is expressed in volts. T h is form ula can also be used when the kinetic
energy o f the electron is expressed in electron volts. F o r V ~ IO4 V (w hich is in
the range o f v o lta g e used in T V tubes), the w avelength is abou t IO- 1 1 no, com ­
parable to the w avelength o f x-rays. T h is means th at if w e send a beam o f fast
electrons through a crystal, w e should obtain diffraction patterns which result from
scattering o f the m atter field. T h ese diffraction patterns, corresponding to the in­
com ing electrons, should be sim ilar to those observed for x-rays.
UO) Particles and fields 35

F ig. 1-21. Diffraction of electrons

by crystal powder (courtesy of Dr.
Lester Germer).

In 1927 the B ritish scientist G. P. T h om son (1892- ) began a series o f

experim ents whose purpose was to study the passage o f a beam o f electrons through
a thin film o f crystalline m aterial. A fte r the electrons passed through the film , th ey
struck a photographic plate, as shown in Fig. 1-20. I f the electrons had behaved
as particles in the m acroscopic sense, a blurred im age would have been observed
because each electron would undergo, in general, a different scattering b y the
atom s in the crystal. H o w e v e r, the result obtained was identical to the D eb ye-
Scherrer patterns for x-ray d iffra c tio n b y a p oly crystal line substance, as indicated
in the photograph o f Fig. 1-21. Sim ilarly, when an electron beam passes through
a single crystal, one obtains L a u e spot patterns (also observed w ith x-rays) as
seen in the photograph o f F ig. 1-22. From the structure o f these patterns one
36 The foundations of quantum physics ( 1.10

Electron
source

S ingle crystal

F ig . 1-23. Davisson and Germer arrangement for observing liragg scattering of

electrons.

can com pute the tie B roglie w avelength λ if one knows the spacing between the
crystal planes and if one applies the formulas that have been d erived for x-rays.
T h e resulting values o f λ can be compared w ith those obtained from Etp (1.46).
T h e result is com p lete agreem ent, w ith in the lim its o f experim ental error.
In the celebrated experim ents b y C. Davisson and L. G erm er (m ade at about
the sam e tim e as those o f Th om son ), a beam o f electrons was sent at an angle to
the face o f a crystal. T h e diffracted electrons w ere observed b y means o f a d etector
sym m etrically located, as indicated in F ig. 1-23. T h is is sim ilar to the B ra g g ar­
rangem ent fo r observing x-ray diffraction. I t was found th at the electron current
registered b y the detector was a maximum e v ery tim e the B ra g g condition, derived
fo r x-rays, was fulfilled. T h e B ra g g condition is expressed b y *

2d sin θ = nX,

where d is the separation o f successive atom ic layers in the crystal, and λ is g iven
b y E q. (1.46).
R ea cto r
shielding
M on oen ergetie
neutn
R ea cto r

Fig. 1-24. Neutron crystal spectrometer.

R o lyen ergetie
neutron Iieam

T h e same phenomenon o f B ra g g diffraction has been observed in experim ents

w ith protons and neutrons. N eu tron d iffraction is especially useful, since it is one
o f the most pow erful means o f studying crystal structure. E xperim enters use
m onoenergetic beams o f neutrons and an alyze th eir passage through the crystal.
T h e neutrons em erging from a nuclear reactor through a porthole (see Fig. 1-24)

* See, for example, Fundamental University Physics, Volume II, Section 23.8.
 Particles and fields 37

liave a w id e spectrum o f energy (in other words, th ey v a r y w id e ly in m om entum ),

or, which is equivalent, the neutron beam is not m onochrom atic; rather it contains
a spectrum composed o f m any de B roglie wavelengths. W h en the neutron beam
from the reactor falls on a crystal, o f L iF fo r example, the neutrons observed in
the sym m etric direction correspond on ly to the w avelength X given b y B ra g g ’s
condition (1.47). T h erefo re th ey have a well-defined energy and m omentum. T h e
crystal then acts as an energy fille r or monochromator. T h e m onoenergetic neutron
beam is in turn used to study other m aterials, b y diffraction, or to analyze nuclear
reactions in vo lvin g neutrons o f definite energy.

E X A M P L E 1.8. What is the de Broglie wavelength of thermal neutrons at a tempera­

ture of 25°C?

S o lu tio n : Ily thermal neutrons we mean neutrons which are in thermal equilibrium with
matter at a given temperature. Thus the neutrons have an average kinetic energy identi­
cal to that of the molecules of an ideal gas at the same temperature. Therefore the average
kinetic energy' of thermal neutrons is Ziove = §kT, where T is the absolute temperature
and k is Boltzmann’s constant (see Eq. 10.41). Given that the temperature is 25°C, we
have T = 298°K and therefore Eove = J k T _ = 6.17 X IO" 21 J = 3.85 X IO-2 eV. The
corresponding momentum is p = V 2mnEave = 4.55 X IO-2 '1 m kg s-1 . Then, using
Eq. (1.44), we find that the average de Broglie wavelength of the thermal neutrons is
X = 1.85 X IO-10 m. (Incidentally', noting that the separation of the planes in a NaCl
crystal is d = 2.82 X IO-10 m, we see that the first diffraction maximum for neutrons
of this wavelength occurs at an angle Θ — 19°.)

E X A M P L E 1.9. An electron is released at a great distance from a proton. Find the

wavelength of the electron when it is (a) I m from the proton, (b) 0.5 X IO-10 m from
the proton (this distance is of the order of magnitude of the radius of the orbit of an
electron in the ground state of a hydrogen atom).

S o lu tio n : The potential through which the electron has moved, when it is at a distance r
from the proton, is

V = e/4ir<0r = 1.44 X IO- iV r V,

where r is in meters. Substituting this value into Eq. (1.46), we find that the wavelength
of the electron is

X = 3.24 X IO-5 V r m.

From this result we note that the wavelength decreases as the electron approaches the
proton. The reason for this is that the electron is accelerated toward the proton, and its
momentum increases as the distance decreases. WTien the electron is I m from the proton,
the wavelength is 3.24 X IO-5 m. When the electron is 0.5 X IO-10 m from the proton
the wavelength is 2.27 X IO-10 m. This wavelength is of the order of magnitude of the
dimensions of the hydrogen atom. However, to accommodate the electron in a stable
orbit around the proton, in a hy'drogen atom, it is necessary’ to adjust its wavelength to
an appropriate value (which is approximately 3.14 X IO-10 m). This requires, as will
be seen later, the loss of a certain amount of energy by the electron, which is emitted as
radiation.
38 The. foundations of quantum physics

F ig. 1-23. Continuous wave train corresponding to an unlocalized particle.

1.11 PartirIeH anti W a rp #*'arhets

U sin g relations (1.44), w e m ay represent the field corresponding to a free particle
m ovin g w ith a well-defined mom entum p and energy E — p 2/'lm by a harm onic
w a v e o f constant am plitude, as shown in F ig. 1-25. S ym m etry demands th at the
am plitude o f the w a ve be the same throughout all space, since there are no forces
actin g on the particle that could d istort the associated m atter field m ore in som e
regions o f space than in others. T h e phase v e lo c ity o f the field o f the free particle is

= χ„ = * £ = E = J L = Iv
p p h p 2m

T h a t is, the phase ve lo c ity o f the m atter field is one-half the particle ve loc ity . T h is
has no experim ental consequence, how ever, since we cannot measure the phase
v e lo c ity o f a pure harm onic w ave directly. W e can on ly measure the group v e lo c ity
o f the waves. (See A p p en d ix I I I . ) T h e fact th at the am plitude o f the m atter field
is the same throughout all space suggests th a t the m atter field o f a free particle
does not g iv e inform ation about the localization in space o f a free particle o f w ell-
defined m omentum. In other words, the m atter field is independent o f the position
o f the particle, anil an observation o f the field b y some m ethod would not reveal
the position o f the particle.
F rom our physical intuition and our knowledge o f fields and waves, w e know that
a particle localized within a certain region A x o f space should correspond to a m atter
field whose am plitude or inten sity is large in th at region and v e ry small outside it.
A field m ay be built up in a certain region and attenuated outside that region
through the process o f interference, b y superposing w aves o f different frequencies
and wavelengths. T h e result is a wave packet, as shown in F ig. 1-2(5. T h e v e lo c ity
w ith which the w a v e packet propagates is the group velo c ity vQ, which is given by
V0 = doi/dlc (see E q. A . 29). Using relations (1.45) and E = p 2/2m, we m ay r e ­
w rite the group v elocity o f the m a tte r field corresponding to a free particle as

vQ— (IE/(Ip = p/m = v.

Thus, just as our physical intuition tells us it should be, the group v e lo c ity o f the
m atter field (i.e., the v e lo c ity o f propagation o f the packet) is equal to the v e lo c ity
 Heisenberg's uncertainty principle 39

F ig. 1-26. W ave packet corresponding to a particle localized within the distance Ax.

o f the particle. W e conclude then th at a particle localized in a certain region o f

space is associated w ith a field or w a v e packet whose am plitude is im portant on ly
in th at reg ion ; the v e lo c ity o f the particle is the group v e lo c ity o f the field or w a ve
packet.

1.12 H e is e n b e rg 's U w e r t a in t y P rin e ip le fo r

P o sitio n a nd M o m e n tu m
N o w w e encounter a special situation which cannot be explained in terms o f classical
mechanics. F o r a w a ve packet to be localized in space, it is necessary to superpose
several fields o f different wavelengths λ (o r w ith different values o f the w a v e num­
ber k ). I f the w ave packet extends o v e r a region Ax, the values o f the w a v e numbers
o f the interferin g w aves which compose the w ave packet and have an appreciable
am plitude fall w ith in a range Ak such that, according to the th eo ry o f Fourier
analysis,
Ax Ak ~ 2ir.

B ut, according to Eqs. (1.44) or (1.45), different wavelengths X or w ave numbers

k mean th at there are several values o f p such that Ap = h Ak. T herefore, when
w e recall th at h = 2irh, the ab ove expression becomes

Ax Ap ~ h. (1-48)

T h e physical m eaning o f relation (1.48) is as follows: I f a particle is w ith in the

region x — % Ax and x + ^ Ax (th a t is, Ax is the uncertainty in the position o f the
p article), its associated field is represented by superposing w aves o f m om enta be­
tween p — $ Ap and p + f Ap, where Ap is related to A x b y relation (1.48). W e
say th at A p is the uncertainty in the m om entum o f the particle. R ela tion (1.48)
im plies th at the larger A x is, the sm aller Ap is, and conversely. In other words,
inform ation about the localization o f a particle in space is obtained a t the expense
o f know ledge about its m omentum. T h e m ore precise our knowledge o f the posi­
tion o f the particle, the m ore im precise is our inform ation about its m om entum ,
and conversely. T h is is w h y a p article o f well-known m om entum (A p = 0 ) is
represented b y a w a ve o f constant am plitude extending o v e r all space (A x ~ oo),
so th at our knowledge o f the position is nil. W e cannot accurately determ ine both
hO The foundations of quantum physics

the position and the m om entum o f a particle simultaneously so th at A x = 0 and

Ap = 0 a t the same tim e. Such knowledge does not conform to relation (1.48).
R elation (1.48) gives the optim um relation am ong the uncertainties A x and Ap in
the position x and the m om entum p o f the particle. H ow ever, in m ost cases x and
p are known w ith less accuracy, so th at w e m ust w rite instead o f relation (1.48) the
m ore general expression

Ax Ap £ h.

T h e result expressed b y relat ion (1.48) is called Heisenberrfs uncertainty prin ciple,
which m ay be stated in w ords as follows:

I l is impossible to knoiv simultaneously and with exactness both the

position and the momentum o f a particle.

T h is principle expresses one o f the fundam ental facts o f nature, and to a certain
exten t m ay be considered as m ore fundam ental than relations (1.45), although
here w e have proceeded in the opposite manner. T o better understand the uncer­
tain ty principle, let us consider some possible physical situations.
T o say th at a particle is a t point x w ith mom entum p means th at we have to
measure simultaneously the coordinate x and the mom entum p, since w ith ou t
measurem ent we d o not have inform ation. B u t if w e an alyze the process o f mea­
surem ent w e note that on the atom ic scale w e cannot measure either the position
or the m om entum w ith out appreciably disturbing the m otion o f the particle. To
1.1-2) Heisenberg's uncertainly principle ill

illustrate, let us consider som e sim ple experim ents. Suppose, for exam ple, th at
w e want to d e te rm in e the .!'-coordinate o f a p article b y observin g w hether o r not
the particle passes through a hole (o f w idth b) in a screen (F ig . 1-27). T h e precision
w ith which w e k n o w the position o f the p a rtic le is lim ited b y the size o f th e hole;
that is, A x ~ b. B u t the hole disturbs the field associated w ith the particle, and
this results in a corresponding change in the m otion o f the particle, as seen b y the
diffraction p a tte rn produced. T h e un certain ty in the p article’s m om entum parallel
to the X -a x is is d eterm ined b y the an gle Θ, correspon din g to the central m axim um
o f the d iffra c tio n pattern, since the particle, a fte r traversing the slit, is m ost prob­
a b ly m o v in g w ith in the angle 2Θ. A c c o rd in g to th e th eo ry o f the diffraction pro­
duced b y a recta n gu lar slit, the angle 0 is g iv e n b y sin θ = A/6. T hen

A p ~ p sin θ = (Λ / λ )(λ/ 6) = Ιι/b

is the u n ce rta in ty in the m om entum parallel to the X -axis. T h erefo re A x A p ~ Λ,

in agreem en t w ith relation (1.48). N o te that to im p rove our a b ility to determ ine
the exact posit ion o f the particle, we m ust use a v e ry narrow slit . But a v e ry narrow
slit produces a v e r y w ide central m axim um in the d iffraction pattern, which means
a large u n certa in ty in our know ledge o f th e X -c o m p o n e n t o f the m om entum o f the
particle. C on v e rse ly , in order to reduce th e u n certain ty in our knowledge o f the
X -com p on en t o f th e m om entum , the central m axim um in the diffraction pattern
must be v e ry narrow . T h is requires a v e ry w id e slit which, in turn, results in a
large u n certain ty in the X -coord in a te o f the particle.
Y

F ig. 1-28. Measurement of position and mo­

mentum of a particle by means of a microscope.

S cattered
lig h t

in ciden t
light

A n oth er experim ent which indicates the im possibility o f observing a particle

w ith out disturbing it is th e case in which w e try to determ ine the position o f an
electron b y means o f a m icroscope (F ig . 1-28). T o observe the electron w e must
illum inate it w ith ligh t o f some w avelength λ. T h e ligh t that passes through the
microscope is th at which lias been scattered b y the electron under observation.
T h e m om entum o f the scattered photons is p photon = Λ/λ, and to penetrate into
the ob jective, th e photons must m ov e w ith in the cone o f angle a, so th at the
42 The foundations of quantum physics ( 1.12

Λ '-com ponent o f th eir m om enta has an uncertainty

Δ ρ ~ Pphoton sin « ~ h d /2\y,

since sin a « d/2y. T h is is also the uncertainty in the X -com p o n en t o f the electron
m om entum a fte r the scattering o f light, since in the scattering process some m om en­
tum is exchanged between the electron and the photon. On the other hand, the
exact p osition o f the electron is uncertain because o f the diffraction o f ligh t when
it passes through the o b je c tiv e o f the microscope. T h e u n certain ty in the position
o f the electron is thus equal to the diam eter o f the central disk in the diffraction
p attern. T h is diam eter is g iv e n b y 2y sin Θ, w ith sin Θ ~ λ /d. * H ence

A x ~ 2y sin Θ ~ 2y\/d.

T h e refo re again A x Ap ~ h. N o te that to im prove the accuracy o f our knowledge

o f the position o f the electron w e must use a radiation o f v e ry small wavelength,
but which produces a large disturbance in the m om entum . Cionverscly, in order
to produce a small disturbance in the m omentum, we must use radiation o f very
lon g w avelength, which in turn g ives rise to a great uncertainty in the position.
T h ese tw o exam ples clearly show that the uncertainty prin ciple is a direct con­
sequence o f the process o f measurement. A t the atom ic level, m easurement in­
e v ita b ly introduces a significant pertu rbation in the system , due to the interaction
between the m easuring d evice and the measured qu antity.
T h e u n certain ty principle im plies th at w e can never define the path o f a particle
with the absolute precision postulated in classical mechanics. Classical mechanics
still holds true for large bodies, such as those o f usual concern to the engineer,
because the uncertainty im plied b y relation (1.48) is much sm aller for a m acro­
scopic b od y than the experim ental errors in the measured values o f x and p for the
body, due to the smallness o f P lan ck ’s constant h. H o w ever, f o r particles o f atomic
dimensions, the concept o f trajectory has no meaning, since it cannot be defined pre­
cisely; therefore a picture o f the m otion different from th a t o f classical physics is
required. P or the same reason, concepts such as v elocity , acceleration, and force
are o f lim ited use in quantum mechanics. On the other hand, the concept o f energy
is o f p rim ary im portance, since it is related m ore to the “s la t e ” o f the system than
to its “p a th ,” as we shall see in the next chapter.
T o describe the dynam ical state o f a particle in a graphical w a y (i.e., its position
and m om entum at each tim e), w e use a representative space, called phase space.
F o r the case o f one-dimensional m otion, the phase space has tw o dimensions, w ith
the abscissa corresponding to the positional coordinate x and the ordinate to the
m om entum p (F ig . 1-29). In classical mechanics the sta te o f a particle is repre­
sented in phase space b y a point w ith coordinates (x, p ), since in classical mechanics
w e can accurately determ ine both position and m om entum sim ultaneously. A s the
p article m oves, the representat ive point describes a line in phase space (F ig . l-2 9 a ).

* W e have disregarded the factor 1.22 which appears in the theory of diffraction of a plane
wave by a circular aperture.
1.13) The uncertainly relation for lime and energy t>3

F ig. 1-29. Classical and quantal path of a particle in phase space.

In quantum mechanics the picture is different. L e t us d iv id e the phase space in to

cells, each cell having sides Δ χ and Δ/> so that Δ χ Ap = A. Th en th e m ost w e can
s a y is that a t each m om ent the represen tative point o f the particle lies w ith in one
such cell. A s tim e goes on, the path o f the represen tative p oin t falls w ith in a
rib b o n lik e path form ed b y patching to geth er a series o f cells (see Fig. l-2 9 b ).

f.1.7 Tliv I 'n vvrta in ty Itvla lion fo r T im v anti Envrfiy

In a d d itio n to the uncertainty relation Δ χ Ap ~ Ii betw een a coordinate and the
corresp on din g m om entum o f a m ovin g particle, there is an uncertainty relation
b e tw e e n tim e and energy. Suppose that w e w ant to m easure not on ly the en ergy
o f a particle but also tbe tim e a t which the p article has such energy. I f Δ< and A E
a r e th e uncertainties in the values o f these quantities, the follo w in g relation holds:

A tA E -Ii. (1.49)

W e can understand this relation in the follow in g w ay. I f w e want to define the
t im e a t which a particle passes through a g iven point w e m ust represent the par­
tic le b y a pulse or w a ve packet h a vin g a v e ry short duration Al. B ut to build such
a p u lse it is necessary to superpose fields which h ave d ifferen t frequencies, w ith an
a m p litu d e appreciable on ly in a frequency range Δ ω centered around the frequency
ω a n d such that, according to the th eory o f F ou rier analysis,

At Δ ω ~ 2π.

M u ltip ly in g b y ft and recalling from E q. (1.4.5) th at E — Ιιω and that 2Trh = h,

w e ob ta in relation (1.49). R elation (1.49) g ives the optim um relation am ong the
u n certain ties Al and AE. H ow ever, in m ost cases, t and E are known with less ac­
c u ra c y , so th at w e m ust w rite instead o f relation (1.49) the m ore general expression

At A E > h.
44 The foundations of quantum physics (1.13

T h e uncertainty relation (1.49) requires that w e revise our concept o f stationary

states. Let us consider an electron in an excited stationary state in an atom . T h e
electron a fte r a certain tim e will suffer a rad iative transition into another station­
a ry state o f less energy. H ow ever, w e have no means o f p redicting w ith certa in ty
how long the electron will remain in the stationary state before m aking the transi­
tion. A s w ill be seen in the next chapter, the most w e can talk about is the prob­
ab ility p er unit tim e that the electron w ill jum p into a low er en ergy state. T h ere­
fore the avera ge length o f tim e the electron is in the stationary state, also called
the lifetim e o f tin; state, and which is inversely proportional to the transition
p rob ab ility w e have m entioned, is known within an uncertainty At. H ence the
energy o f the stationary state o f the electron is not known precisely but has an
uncertainty Al'J, such that relation (1.49) holds. O ften A E is designated as the
energy width o f the state whose energy is m ost probably between E — \ A E and
E T h A E (F ig . 1-30). W e m ay assume that Δ/ is o f the order o f m agnitude o f the
lifetim e o f the excited state. Thus, the shorter the lifetim e o f an excited state, the
larger the uncertainty in the energy o f the state. F o r the ground state, whose
life t im e is in fin ite hecAtiso n s vsto m w h ich is A t its Around s ta te C a n n o t s u ffe r a
- cc. T h is yield s
ccurately.

G round state

F ig. 1-30. Width of energy levels.

Because o f the energy w idth o f station ary states, the energy released or ab-
sorbed in a transition is not well defined. Thus in a transition between states o f
en ergy E i anil E 2, the photons em itted or absorbed fall in the energy range

E 2 — L· I ± h Al·.,

w here A E is the total energy w idth o f both states.

 V
i.13) The uncertainly relation for lime and energy 45

A further broadening o f the energy o f the stationary states is caused b y the

electrom agnetic D op p ler shift. T h e atom s o f a substance are in m otion, some
advancing tow ard and some retreating from the observer, and the observed fre­
quency o f the radiation em itted b y the atom differs according to the direction o f
relative m otion. In m ost atom ic and m olecular transitions, the broadening due
to the D op p ler effect is much greater than the broadening due to the uncertainty
principle, but is usually sm aller for nuclear transitions.

E X A M P L E 1.10. The possibility of resonance absorption in atomic and nuclear transi­

tions as a result of the energy width of the stationary states.

S o lu tio n : In Example 1.6 we saw that in a transition between states of energies E i and
# 2, the photon emitted or absorbed has an energy which is smaller or larger, respectively,
than Eo — E i by an amount (E 2 — E i ) 2/2M c2. Therefore, if the energy width X E is
larger than (Eo — E i ) 2/2.1/c2, photons emitted by one system can be absorbed by an­
other of the same kind; but if X E is smaller, the absorption does not necessarily occur.
The first situation is normally found in atomic and molecular systems and the second is
more common in nuclei. For example, in the atomic case of the 4.86 eV transition in
mercury, mentioned in Section 1.8, the lifetime of the excited state of mercury is about
10~s s. A mercury atom, whose atomic mass is about 200 amu or 3.34 X IO-25 kg, has
a rest energy M c2 = 1.86 X IOn eV. Therefore the term accounting for the atomic
recoil with Eg — E i = 4.86 eV is

^ 7| ^ = 7 .1 5 X 1 0 - , l eV.

The uncertainty in the energy of the mercury atom excited level, which has a lifetime
Xl ~ IO" 8 s, is X E ~ h/Xt = 4.14 X IO-7 eV. This is much larger than the correction
term, by a factor of about IO4. From this typical example we may thus conclude that
recoil effects due to momentum conservation in atomic and molecular transitions do not
hinder resonance absorption.
As an example of a nuclear transition, consider the case of the 1.33 M eV gamma ray
emitted by 00N i. A nickel atom, whose atomic mass is about 60 amu or I X IO-25 kg,
has a rest energy M c2 = 5.61 X IO10 eV. Also E? — E i = 1.33 X 10® eV. Therefore
the correction term which accounts for the nuclear recoil is (E 2 — E i ) 2/2M c2 = 15.8 eV,
which is relatively larger (compared with E 2 — E i) than in the atomic ease. The Iife-
tinte of the nuclear excited state is Xt ~ IO-14 s. Hence the uncertainty in the energy
of the excited level is X E ~ h/Xt = 0.414 eV, which is smaller than the correction term
by a factor of about 38. Therefore recoil effects due to momentum conservation in nuclear
transitions are important. These effects make it impossible, in many cases, for a nucleus
to absorb the gamma photon emitted by another similar nucleus.

E X A M P L E 1.11. Discussion of the Mossbauer effect.

S o lu tio n : In the previous example we saw that in nuclear transitions the energy uncer­
tainty due to the finite life of an excited nuclear state is much less than the recoil energy
of the nucleus, thereby making it impossible for a Ύ-ray photon emitted by a nucleus to
be absorbed by another identical nucleus. However, under special circumstances, recoil
effects can be reduced by a large factor. This is possible when the emitting and absorbing
46 The foundations of quantum physics

nuclei are bound in a crystal lattice and the conditions are such that the whole crystal
recoils, instead of just a single atom recoiling. Then the mass is so large that the recoil
energy is very small compared with E 2 — E j. Thus resonance absorption may occur,
resulting in the so-called Mossbauer effect, which was observed for the first time in 1958
by the German physicist R. L. Mossbauer.

j t
j · 'V Absorber
F ig . 1-31. Experimental arrange­ Iψ "ιγ _ /r^I)etector
ment for measuring the width of an
energy level.

The Mossbauer effect has been used to investigate several important physical proper­
ties. For example, by means of the arrangement of Fig. 1-31, the natural energy width
A E of a nuclear state can be determined. A 7-ray source is mounted on the rim of a turn­
table whose velocity can be adjusted. When the source is at .1 its radiation passes through
the hole in the shielding and falls on an absorber, which is composed of atoms of the same
material as the source. Both emitter and absorber are embedded in crystals to essentially
eliminate recoil effects. When the emitter is at rest relative to the absorber, resonance
absorption is observed. But if the turntable is set in motion resonance absorption becomes
impossible. This is due to the Doppler shift in the frequency of the emitted 7-ray as a
result of the motion of the source relative to the absorber.

Absorption curve

Fig. 1-32. Detector current as

a function of the turntable rim
velocity.
-8 -6 -4 -2 0 +2 +4 +G +8
I), cm s“ 1

Figure 1-32 shows the intensity of the transmitted radiation. Note that maximum
absorption occurs at zero relative velocity, and that the absorption decreases when the rel­
ative velocity increases in either direction. For a relative velocity of about 4 cm s-1 , corre­
sponding to a change in the Doppler frequency of about Av ~ v(v/c) = 1.33 X IO- l l V,
or a change of energy A E ~ 1.33 X IO- l o Zi1absorption is practically negligible, indicating
that the energy width of the state is about half as great.
 Problems 47

K e fe re n c e e

1. “ E arly Work in Electron Diffraction,” G. Thomson, Am. J . Phys. 29, 821 (1961)
2. “ T h e Scattering of X-rays as Particles,” A. Compton, Am. J . Phys. 29, 817 (1961)
3. "E instein’s Proposal of the Photon Concept,” A. Arons and M . Peppard, Am. J.
Phys. 33, 367 (1965)
4. “ 60 Years of Quantum Physics,” E. Condon, Physics Today, October 1962, page 37
5. “ Paths to Quantum Theory Historically Viewed,” F. Hund, Physics Today, August
1966, page 23
6. “ T h e Mossbauer Effect,” S. de Benedetti, Sci. Am., April 1960, page 72
7. Introduction to Modern Physics, F. Richtmyer, E. Kennard, and T . Lauritsen. New
Y o r k : McGraw-Hill, 1955, Chapter 3, Sections 43, 44, 49-55; Chapter 4; Chapter 5,
Sections 86 and 87; Chapter 6, Sections 90-95
8. Great Experiments in Physics, Morris Shamos, editor. N ew Y ork : Holt, Rinehart, and
Winston, 1959, Chapter 17 (Einstein); Appendix 2 (Planck); Appendix 5 (Compton)
9. The Feynman Lectures on Physics, Volume I, R. Feynman, R. Leighton, and M . Sands.
Reading, M ass.: Addison-Wesley, 1963, Chapter 37
10. Foundations of Modern Physical Science, G. Holton and D. H. D. Roller. Reading,
M ass.: Addison-Wesley, 1958, Chapters 31 and 32

i*r o b le m s

1.1 When an electron is accelerated 1.4 I t can be shown from M axwell’s

through a potential difference of I volt
its gain in kinetic energy is called I elec­
tron vo lt (eV ). (a) Show that I eV =
1.602 X IO- l o J. (b) W hat is the energy
increase of an electron when it is acceler­
ated through 10 V, 50 kV, and I M V ?
(c) Assuming that the electron starts from
rest, calculate the final velocity.
1.2 A gaseous source emits light of wave­
length 5 X IO-7 m. Assume that each
molecule acts as an oscillator of charge e
and amplitude IO-10 m. (a) Compute the
average rate of energy radiation per mol­
ecule. (b) I f the total rate of energy radi­
ation of the source is I W, how many
molecules are emitting simultaneously?
1.3 Estimate the value of (dE/dl)aye as
given by Eq. (1.5) for a proton in a nu­
cleus. Assume Zn of the order of IO-15 m
and ω about 5 X IO20 Ilz for low-energy
gamma rays.
equations that the electric and magnetic
fields in a plane electromagnetic wave are
related by 8 = cffi. Show that the energy
density in the wave may be written as
E = «o8 2. The intensity I of the wave is
equal to the energy flowing, per unit time,
across a unit area perpendicular to the
direction of propagation. Show that
I = ceo62.
1.5 The momentum density in an elec­
tromagnetic wave may be written /> =
eo£ X (B. Show that this expression has the
units of momentum per unit volume. Also
show that for a plane wave, E = pc.
[M int: Recall the relation between 8 and <B
in a plane wave and the expression for E
given in Problem 1.4.)
1.6 Electromagnetic radiation from the
sun falls on the earth’s surface at the rate
of 1.4 X IO3 W m -2 . Assuming that this
radiation can he considered as a plane wave,
estimate the magnitude of the electric and
magnetic field amplitudes in the wave and
the momentum density of the wave, (b)
I f this momentum is absorbed by the
earth’s surface, compute the radiation
pressure on the earth.
1.7 Radio w aves received by a radio set
have an electric field of amplitude equal
to IO-1 V m -1 . Assuming that the wave
can lie considered as plane, calculate:
(a) the am plitude of the magnetic field,
(b) the average intensity of the wave,
(c) the average energy density, (d) the
average niomcn turn density. (e) As­
suming that the radio set is I km from the
broadcasting station and that the station
radiates energy isotropically, determine
the power of th e station. [H int: Recall
that if the electric field varies harmonically
with an am plitude Go, the time average of
the square of the field is 2Gq.]
1.8 Show that th e intensity of the radia­
tion coming from a small hole in the walls
of a cavity which is in thermal equilibrium
with the radiation (i.e., a blackbody) is
given by I = yc t o , where E is the radiation
energy density. A.lso show that the Stefan-
Boltzmann constant is σ = \ca, where
a = 7.56 X IO- l e J Iii- 30K -4 (see Ex­
ample 1.4).
1.9 W rite the asym ptotic form of Planck’s
radiation law (E q . 1.8), for a case in which
the frequency is very high and one in
which it is very lo w . The first relation is
called Il'ien’s radiation law and the second
is called the Rayle-igh-Jcans radiation law.
1.10 W hat is the wavelength correspond­
ing to the peak of the blackbody radiation
spectrum at 800° K (room temperature)?
Determine the monochromatic energy den­
sity at this wavelength.
1.11 Assuming th a t the sun is a spherical
blackbody with a. radius of 7 X 10s m,
calculate the sun’ s temperature and the
radiation energy d en sity within it. The
intensity of the s u n ’s radiation at the sur­
face of the earth (which is 1.5 X IO11 111
distant from the s u n ) is 1.4 X IO3 W m -2 .
Are the numbers evaluated realistic?
Explain.
1.12 The photoelectric work function of
potassium is 2.0 eV. Supposing that light
having a wavelength of 3.6 X IO-7 m
falls on potassium, find: (a) the stopping
potential of the photoelectrons, (b) the
kinetic energy and the velocity of the fast­
est electrons ejected.
1.13 A uniform monochromatic beam of
light, of wavelength 4.0 X IO-7 m falls
on a material having a work function of
2.0 eV. The beam has an intensity of
3.0 X IO- e W m -2 . Find: (a) the num­
ber of electrons emitted per m2 and per s,
(b) the energy absorbed per m2 and per s,
(c) the kinetic energy of the photoelectrons.
1.14 The binding energy of an inner elec­
tron in lead is 9 X IO4 eV. When lead is
irradiated -with a certain electromagnetic
radiation and the photoelectrons enter a
magnetic field of IO-2 T , they describe a
circle of radius 0.25 m. Compute: (a) the
momentum and energy of the electrons,
(b) the energy of the photons absorbed.
1.15 When a certain metal surface is illu­
minated with light of different wavelengths,
the stopping potentials of the photoelec­
trons are measured as shown in the table.
λ (Χ IO-7 m) V, V λ (Χ IO-7 m) F 1V
3.66 1.48 ,4.92 0.62
4.05 1.15 5.46 0.36
4.36 0.93 5.79 0.24
Plot the stopping potential as ordinate
against the frequency of the light as ab­
scissa. From the graph determine: (a) the
threshold frequency, (b ) the photoelectric
work function of the metal, (c) the ratio
h/e.
1.16 A photon having an energy of IO4 aV
collides with a free electron at rest and is
scattered through an angle of 60°. Find:
(a) the changes in energy, frequency, and
wavelength of the photon, (b) the kinetic
energy, momentum, and direction of the
recoiling electron.

1.17 Radiation having a wavelength of
10" 10tn (or I A ) undergoes Compton
scattering in a carbon sample. The scat­
tered radiation Ih observed in a direction
perpendicular to that of incidence. Find:
(a) the wavelength of the scattered radia­
tion, (b) the kinetic energy and direction
of motion of the recoil electrons.
1.18 Referring to the preceding problem,
if the electrons recoil at an angle of 60°
relative to the incident radiation, find: (a)
the wavelength and direction of the scat­
tered radiation, (b) the kinetic energy of
the electron.
1.19 Find the energy and wavelength of a
photon that can impart a maximum energy
of 60 kcV to a free electron.
1.20 A beam of monochromatic x-rays
with a wavelength of IO-11 m strikes a
thin metal foil. The scattered radiation
is observed at angles of (a) 90° and (b) 60°.
What two predominant frequencies will be
detected in each case?
1.21 Show that when a free electron is
scattered in a direction making an angle
φ with the incident photon in a Compton
scattering, the kinetic energy of the elec­
tron is
E t = hv(2ct cos2 φ )/ [(I + a )2 — a 2 cos2 φ],
where a = hv/» icc2.
1.22 Show that, in a Compton scattering,
the relation between the angles defining
the directions of the scattered photon and
the recoil is cot φ = ( I + a) tan \θ, where
a = IivZmcC2.
1.23 A monochromatic beam of electro­
magnetic radiation has an intensity of
I W m - 2 . What is the average number
of photons per m3 for (a) 1-k IIz radio
waves and (b) IO-MeV gamma rays?
1.24 The minimum light intensity that
can be perceived by the eye is about
IO- 1 0 W m -2 . How many photons per sec­
ond (wavelength 5.6 X IO-7 m) enter the
pupil of the eye at this intensity? T hcpupil
area may be considered as 0.5 X IO-4 m2.
Problems 49
1.25 Determine the frequency and the
wavelength of the photons absorbed by
the following systems: (a) a nucleus ab­
sorbing energy in the amount of IO3 eV,
(b) an atom absorbing I eV, (c) a molecule
absorbing IO-2 eV.
1.26 Sodium atoms absorb or emit elec­
tromagnetic radiation of 5.9 X IO-7 m,
corresponding to the yellow region of the
visible spectrum. Determine the energy
of the photons which arc absorbed or
emitted.
1.27 (a) The longest wavelength that can
produce resonance radiation in mercury is
2.536 X IO-7 m. What is the first excita­
tion potential of mercury? (b) The emis­
sion spectrum of mercury shows strong
lines at wavelengths of 1850 A, 2536 A,
3132 A, 5460 A, and 5780 A. There are also
weak lines at 1402 A and 12072 A. Calcu­
late the energy of these transitions and
set up an energy level spacing similar to
Fig. l —15(b), knowing that the 2536 A
line is associated with the excitation from
the ground state to the first excited state.
1.28 The sodium I) lines (see Problem
1.26) appear when sodium is bombarded
by electrons when they are accelerated by
a potential difference of 2.11 volts. Com­
pute the value of li/e.
1.29 T o separate the carbon and oxygen
atoms that form the carbon monoxide
molecule, a minimum energy of 11 eV is
required. Find the minimum frequency
and maximum wavelength of the electro­
magnetic radiation required to dissociate
the molecule.
1.30 A photon having an energy of IO4 eV
is absorbed by a hydrogen atom at rest. As
a result, the electron is ejected in the same
direction as the incident radiation. N eg­
lecting the energy required to separate the
electron (about 13.6 eV ), find the momen­
tum and the energy of the electron and of
the proton.
1.31 What is the shortest bremsstrahlung
wavelength observed when an electron ac­
celerated through a potential difference of
40 kV is suddenly stopped at the anti­
50 The foundations of quantum physics
cathode of an x-ray tube? Determine the
region of the electromagnetic spectrum in
which this wavelength lies by referring to
Fig. 1-13.
1.32 In the upper atmosphere molecular
oxygen is dissociated into tw o oxygen
atoms by photons from the sun. The max­
imum photon wavelength which causes
this process is 1.75 X 10“ 7 m. W hat is the
binding energy of Oa?
1.33 Correct Kqs. (1.40) and (1.41) to
take into account the recoil effect of the
ion. Using the corrected equations, com­
pute the minimum energy a photon must
have to ionize the hydrogen atom.
1.34 Show that, in the recombination
process, A + + e —* Λ is impossible with­
out violating either the conservation of
energy or momentum, unless there is a
third particle.
1.35 Prove that, in Eq. (1.42), conserva­
tion of momentum and energy would be
impossible if there were not matter (a
nucleus at least) present.
1.36 Λ 2.9-MeV photon, passing through
lead, creates an elcctron-positron pair.
The particles have equal kinetic energies.
Find: (a) the momentum, (b) the energy,
and (c) the velocity of each. N eglect the
recoil energy of the lead atom.
1.37 W h at is the greatest possible number
of positrons that may he created by a 130-
M eV photon as it passes through a
material?
1.38 Gamma rays with energies of 0.05,
0.3, and I M eV, hut with equal intensities,
are incident on a lead absorber. T h e linear
absorption coefficients for these energies
are 8 X IO3 m - 1 , 5 X IO2 m _ l , and 78 m -1 ,
respectively, (a) Calculate the thickness of
lead necessary to reduce the intensity of
each beam -to one-tenth its original inten­
sity. (b) What is the ratio of the total
intensity (of all three photon energies), at
a depth of 5 mm, to the total incident
intensity?
1.39 The half-value thickness X \ /2 is defined
as the thickness an absorber must have to
reduce the intensity of an incident beam
of x-rays to one-half its original intensity.
Show that x I /2 = In 2/Σ. Find the half­
value thickness of lead for 0.1, 0.5, and
I M eV x-rays. [Hint: Refer to Fig. 1-19
for the coefficients of linear absorption.]
1.40 X-rays are passed through aluminum
foils, each of thickness 4 X IO-3 m. T h e
counting rate of a Geiger counter as a
function of the number of foils is 8 X IO3,
4.7 X IO3, 2.8 X IO31 1.65 X IO319.7 X IO2
counts/min forO, I, 2, 3, and 4 foils, respec­
tively. Calculate the linear absorption
coefficient of aluminum. From Fig. 1-19,
estimate the energy of the x-rays.
1.41 IIow many half-value layers of a
material are necessary to reduce the in­
tensity of an x-ray beam to (a) yg, (b) 55 ,
and (c) jJ-jj of its incident value?
1.42 Calculate the de IirogIie wavelength
of an electron when its energy is I eV,
100 eV, 1000 eV. W hat wavelengths
would be significantly diffracted in a
nickel crystal, in which the atomic separa­
tion is about 2.15 A? Calculate the energy
of those electrons which are Bragg-dif­
fracted at an angle of 30°.
1.43 Monochromatic x-rays (λ = i A )
are incident on a sample of K C l powder.
A flat photographic plate is placed per­
pendicular to the incident beam, a dis­
tance of 1.0 m from the powder. Deter­
mine the first- and second-order Bragg
radii, given that the Bragg plane separa­
tion is 3.14 A.
1.44 A narrow beam of thermal neutrons
produced by a nuclear reactor falls on a
crystal with lattice spacing of 1.60 A.
Determine the Bragg angle such that 2 eV
neutrons arc strongly diffracted.
1.45 Show that the ratio of the de Broglie
wavelength to the Compton wavelength
for the same particle is equal to
V t c /νμ - I.
1.46 Verify the fact that the group veloc­
ity of a wave packet is equal to the particle
 Problems 51

velocity, even under relativistic condi­ differ by the constant amount A. Relate
tions. Also show that the phase velocity with the explanation associated with
of the matter field at relativistic speeds is Fig. 1-29.
equal cf/v. 1.52 Find the line width and frequency
1.47 Suppose that a beam of electrons spread for a 1-nanosecond ( 10- 9 s) pulse
with a de Broglie wavelength of IO-5 m from a ruby laser (λ = 6.3 X IO-7 m).
passes through a slit IO-4 m wide. What 1.53 I f a source moves with a velocity u,
angular spread is introduced because of relative to an observer, the frequency of
diffraction by the slit? the radiation measured by the observer
1.48 A probe must always be smaller (at suffers a shift Av = vu/c, where u is posi­
least by a factor of 10) than the object tive (negative) when the motion is toward
being studied; otherwise there will be (away from) the observer, and where v
significant perturbation of the position would be the frequency if the source were
and velocity of the object. Calculate the stationary. This is called the electromag­
minimum particle energy if (a) photons, netic Doppler shift. Since the molecules in
(b) electrons, (c) neutrons are used to probe a gas are in random motion, the Doppler
a nucleus whose diameter is IO-14 m. shift is different for each molecule. This
1.49 The velocity of a proton in the.Y-direc- introduces a line broadening, given by
tion is measured to an accuracy of IO-7 S = 2(v/c)\/2kT In 2/m, where m is the
m s-1 . Determine the lim it of accuracy mass of the molecule and T is the absolute
with which the proton can be located temperature of the gas. Compute the Dop­
simultaneously (a) along the A'-axis, pler broadening at room temperature
(b) along the K-axis. Repeat for a case (300°K) for the 4.86-eV atomic transition
in which the particle is an electron. in mercury and for the 1.33-MeV nuclear
1.5(1 The position of an electron is deter­ transition in eoN i. Discuss in each case
mined with an uncertainty of 0.1 A. Find the effect on resonance absorption.
the uncertainty in its momentum. If the 1.54 The gamma-ray line emitted by 101Ir
electron’s energy is of the order of I ke^V, has a mean energy of 129 keV and the mea­
estimate the uncertainty in its energy. sured width of the line at half-maximum
Repeat for a proton confined to a nuclear intensity is 4.6 X IO-6 eV. Estimate
diameter ( = 10-14 m) with an energy of (a) the mean lifetime of the excited state
the order of 2 MeV. emitting this line, (b) the relative velocity
1.51 Show that the path in phase space of of source and observer which is required
the point representing a harmonic oscillator to give a first-order Doppler shift equal to
of angular frequency ω is an ellipse of semi­ the measured line width.
axes A and m u A 1 where m is the mass of 1.55 Show' that the maximum change
the oscillator and A is the amplitude of its in kinetic energy of a particle of mass m,
motion. Find the area of the ellipse and with initial kinetic energy E k, when it col­
show that it is equal to 2πΕ/ω, where E is lides with a particle of mass .1/ initially at
the total energy of the oscillator. Compar­ rest in the Λ-frame is A E k = — 4Λ E k/
ing this value with Eq. (1.7), verify that (1 -f- .-I)2, where .1 = M/m. (a) Find the
the area of an allowed ellipse is nh, and limiting value when M » m. (b) Plot
hence the areas of two successive ellipses A E k as a function of A .
 2
QUANTUM MECHANICS

2. I In lro d u d io n
2.2 Wave Fu nclion and Probabilily Density
2.3 Sdirodinger s Equalion
2/i P olen tial Step
2.5 P article in a Potential B ox
2.6 The H arm onic Oscillator
2.7 Energy Levels and Wave Functions in General
2.S Potential B arrier Penetration
2.9 Symmetry, U are Functions, and P a rity
2.10 The Time-Dependent Schrbdinger Equation
2.11 Tran sition Probabilities and Selection Rules
2.12 The Form al Theory o f Quantum Mechanics
2.2) Wave function and probability density 53

2.1 lntroth irtion

T h e mention o f the bodies w e observe around us can be described (independently
o f the interactions am ong them ) in terms o f general rules based on experim ental
evidence. T h ese rules or principles are: ( I ) the conservation o f m om entum , (2 ) the
conservation o f angular m omentum, and (3 ) the conservation o f energy. Based on
these conservation laws, a formalism , called classical mechanics, was developed for
describing the detailed m otion o f particles, under the assumptions th at the p arti­
cles are localized in space and th a t w e can observe them w ith ou t appreciably dis­
turbing their m otion. These assumptions are, in general, m ade im plicitly, rather
than stated in a precise w ay. T h is formalism has been used to describe and an alyze
the m otions o f various bodies, ranging in size from planets a t one extrem e dow n to
electrons at the other. H ow ever, when applied to the m otion o f the basic constitu­
ents o f m atter, classical mechanics gives on ly approxim ate results; in some instances
it is en tirely inadequate.
W e saw in the preceding chapter that, as a result o f experim ental evidence, w e
have been forced to introduce several new and revolu tion ary concepts into our
m ethods for describing the beh avior o f m atter. A lth ou gh the laws o f conservation
o f m om entum , angular m om entum , and energy remain valid, the uncertainty
principle forces us to renounce any detailed description o f the m otion o f atom ic
particles in the sense o f classical mechanics. T h e quantization o f energy (and per­
haps o f other physical quantities) is another novel idea which does not appear in
classical mechanics. A satisfactory th eory must contain inform ation abou t the
allow ed energy levels. T h e interaction o f radiation and m atter by means o f the
absorption or emission o f photons is another new concept to be incorporated.
T h erefo re the situation has required that we develop a new formalism, called
quantum mechanics, w hich has produced a profound revolution in physics. Quan­
tum mechanics in its present form is the result o f the w ork o f Louis de B roglie,
E rw in Schrodinger, W ern er Heisenberg, Paul D irac, M a x B orn, and others who
d eveloped it in the late 1920’s. Quantum mechanics is essential for the under­
standing o f the b ehavior o f the fundam ental constituents o f m atter. T h e th eory
is m athem atically elaborate, but its basic ideas are rela tiv ely simple. In this chap­
ter w e shall briefly discuss some fundam ental aspects o f quantum mechanics,
enough so th at we shall be able to a p p ly the th eory to the analysis o f atom ic,
molecular, and nuclear structure, which w ill be considered in the follow ing chapters.

2 .2 W a r r F u n rtio n anti F ro b n h ilitu llrn sity

In Section 1.12 we concluded th at w e cannot talk about the trajectory o f an
atom ic p article in the sense o f classical mechanics. W e cannot, for example, ask
w hether or not the electrons m ove in ellip tica l orbits around the nucleus in an
atom . T h is question would be meaningless even if the forces actin g on the particles
produced such classical orbits. B u t if we cannot talk about the trajectory o f an
electron or o f an y other atom ic particle, how m ay we describe its m otion?
T h e inform ation to answ er this question is provided b y the matter field, which
was introduced in Section 1.10. T o obtain such inform ation, we are guided by our
know ledge o f standing w aves; i.e., w aves confined to a certain region such as a
54 Quantum mechanics (2.2

vib ra tin g string w ith fixed ends, an oscillating air column closed a t both ends, or
electrom agnetic radiation trapped in a c a v ity which has perfectly conducting walls.
W e recall th at in standing w aves the amplitude o f the w ave is fixed a t each point
o f space. A t points where the am plitude is larger, the w a v e is m ore intense.
A sim ilar situation occurs in the case o f atom ic particles. Consider, for example,
an electron in an atom . I t never m oves too far aw a y from the nucleus; it is essen­
tia lly confined to a small region o f space w ith dimensions o f the order o f IO- 9 m.
Thus its associated m atter field m ay be expressed in term s o f standing w aves local­
ized in this region, w ith the am plitude v aryin g from point to point within the region
and being practically zero outside this region. L e t us designate the am plitude o f
the m atter field b y Φ (χ). T h is am plitude φ (χ ) is currently called the wave fu n ction
for historical reasons, although the name is m isleading. Perhaps it would be b etter
ju st to call it the malter-field amplitude.
W e know th at the intensity o f a w a v e m otion is proportional to the square o f the
am plitude. T h erefo re the intensity o f the matter field is given by |ψ(.τ)|2. T h e w ave
function φ {χ ) is som etimes expressed b y a com plex function; th at is, a function
containing i = y / — I. T h e com plex conjugate o f a com plex function is obtained
b y replacing each i by — i. T h e com plex conjugate o f a function φ is designated by
φ *. T h e n \Φ(χ) \ 2 = φ * (χ )φ (χ ). F o r a real function φ = φ*. N e x t w e shall con­
sider what physical m eaning is ascribed to the intensity o f the m atter field. Since
the m atter field describes the m otion o f a particle, w e m ay say th at the regions o f
space in which the particle is more likely to be found are those in which \φ(χ) \ 2 is large.
F o r exam ple, the w a ve function φ (χ ) for a p article confined m ainly to the region
between A and B is shown in Fig. 2-1 (a ). N o te that φ (χ ) decreases v e ry rapidly
outside the region A B where the p article is lik ely to be found while the w a v e func-

— ΛΓ

(b)

Fig. 2-1. (a) W ave function of a particle moving between A and B. (b) Probability
distribution corresponding to the wave function shown in (a).
2.2) IFare Junction and probability density 55

tion isjoscillatin g in such a region. T h e intensity o f the m atter field, given b y

\ i(x )\ 2, is indicated in F ig. 2 - l ( b ) . T o be m ore qu an titative, let us say that

the probability o f fin d in g the particle described by the leave fu n ctio n f ( x )

in the interval dx around the poin t x is |^(x)|2 dx.

In other words, the prob ab ility per unit length (o r probability density) o f finding
the particle at x is

P (x ) = \φ(χ)\2.

W e are assuming, for sim plicity, th at the m otion is in one direction only. B u t in
the general case o f motion in space, the w a v e function (o r m atter-field am plitude)
depends on the three coordinates x, y, z {th at is, f ( x , y, z)]. T h e n |ψ(χ, y, z)|2 dx dy dz
is the prob ab ility o f finding the particle in the volum e dx dy dz around the p oin t
h aving coordinates x, y, z, or

P = |* (χ ,ν ,* )|* (2D

is the p rob ab ility per unit volum e, or the probability density, o f finding the particle
a t x, y, z. F o r exam ple, suppose th at w e com pute ψ (χ, y, z) for an electron in an
atom , and plot \ i \2 as in Fig. 2-2, where N is the nucleus and the degree o f dark-

F ig. 2-2. Probability distribution for an electron in an atom.

56 Quantum mechanics (2.3

ness is proportional to the value o f \φ(χ, y, z)|2. Thus the darker zones represent
the regions in which the p rob ab ility o f finding the electron is greatest. T h is state­
m ent is the m ost we can say about the localization o f the electron in the atom , and
it is im possible to talk about the precise orb it o f the electron.
T h e p rob ab ility o f finding the electron w ith in a finite volum e V is obviously

Pv = J \Φ(χ, y, z )I2 dx dy dz.

N o w the electron must always be som ewhere in space, and therefore if w e extend
the a b o v e integral to all space the prob ab ility becomes certain ty or I. Then we
must have

ί \φ(χ, y, z)\2 d x d y d z = I. ( 2.2)

J A ll space

T h is expression is called the norm alization condition. I t imposes a severe lim itation
on the possible forms o f the w ave function φ (χ , y, z), since it is not alw ays possible
to satisfy E q. (2.2) for an arb itrary function. In particular, φ (χ , y, z ) must decrease
v e ry rapidly when the coordinates x, y, z are v e ry large, in order for the integral
over all space to exist.

2 .:I Sehroiiini/or'H Kiination

Our next step must be to find a rule by which the field am plitude or w ave function
φ can be obtained for each dynam ical problem . O bviously the w a ve function φ (χ )
must depend on the dynam ical state o f the particle. T h is dynam ical state is deter­
m ined b y the forces actin g on the p article and b y the particle’s total energy. B u t
if the forces are conservative, the m otion is determ ined by the potential energy
E p(x ) o f the particle. Thus w e m ay expect th at the w a v e function φ (χ ) must
depend in som e w a y on the potential energy and the total energy, *

E = P 1I l m + E p(x ),

o f the particle. In fact, the rule fo r finding φ (χ ) is expressed in the form o f a d if­
ferential equation, called Schrodinger’s equation, which was form ulated in 1926 b y
th e G erm an physicist E rw in Schrodinger (1887-1901). T h is equation (fo r one­
dimensional problem s) is

- £ S +e - e*·<
2*
where m is the mass o f the particle. Schrodinger’s equation is as fundam ental to
quantum mechanics as N e w to n ’s equation F = dp/dl is to classical mechanics or
M a x w e ll’s equations are to electrom agnetism . O bviously the solut ions φ o f E q. (2.3)
depend on the form o f the poten tial energy E p(x ).
W e shall not m ake a detailed derivation o f Schrodinger’s equation, since that
would be beyond the scope o f this book. Instead we shall ju s tify it in E xam ple 2.1
2.3) Schrodinqer's equation 57

in an in tu itive manner, b y an alogy w ith other fields m ore fam iliar to the student.
Also, in Section '2.12, w e shall indicate, w ith in the form al context o f quantum
mechanics, how the equation is obtained.
In the case o f a free particle the potential energy is zero (th a t is, E p(x ) = 0),
and Schrodinger’s equation becomes

_ *1 = E i
2 m dx2 ψ

which m ay be w ritten in the form

^ + o. (24)
dx2 h2

B u t for a free particle, E = p 2 /2m. S ettin g p = hk,according to Eq. (1.45), where

k is the w a v e number, w e have E = I r Ic2 / 2 m.T h en E q. (2.4) becomes

g + (V - 0. (2.5)

which is identical to the equation for the am plitude o f standing w aves w ith a w a ve­
length λ = 2 ir/k = h/p, as required by E q. (1.44). T h is equation is obeyed, for
example, by the am plitude o f standing w aves on a string or in a gas column or
electrom agnetic w aves trapped in a c a v ity .*
R em em bering th at i = \/— I and i 2 = — I , w e see, b y direct substitution, that
the differential equation (2.5) adm its as solutions the w a v e functions

φ (χ ) = eikz and φ (χ ) = e ~ ikx. ( 2.0)

A s w e shall see in Section 2.10, the w ave function φ = e 'kx represents a free p arti­
cle o f m om entum p = hk and energy E = p 2 /2 m = h 2 k 2 /'2m m ovin g in the
+ A -direction, and the w a v e function φ = e ~ 'kx represents a free particle o f the
same m om entum and energy but m ovin g in the opposite or — X -direction.
T h e general solution o f E q . (2.5) can be w ritten as a linear com bination o f the
tw o solutions given in E q. (2 .6 ); th at is,

φ (χ ) = A c ikx + B e ~ ikz. (2.7)

T h is w a v e function does not correspond to a preferred direction o f m otion, but is

the superposition o f the solutions for m otion in the + A - and —A’ -directions. T h is
is the same situation found in standing waves. (R eca ll, for exam ple, that standing
w aves on a string result from the superposition o f waves propagating in both
directions and reflected at the fixed ends.)
N o te th at E q. (2.6) yield s

|*(.r) [ 2 = φ * (χ )φ (.r) = e ~ ikz ■ eikx = I.

* See Fundamental University Physics, Volume II, Sections 22.4 through 22.9.
58 Quanlum mechanics ( 2.3

T h e fact th at |Ά(χ)|2 = I, or a constant, means that the p rob a b ility o f finding the
particle is the same at an y point. In other words, φ = describes a situation
in which w e h ave com plete uncertainty about position. T h is is in agreem ent w ith
the un certain ty principle, because ψ = e±,kz describes a particle whose m om entum ,
p = hk, w e know precisely; th at is, Ap = 0, which requires th at A x —> x . T o ob­
tain inform ation about the position o f a p article localized w ith in a region A r, w e
m ust therefore superpose several solutions o f the form A e ikx, w ith different values
o f k (o r p ), and w ith appreciable am plitude Λ in a range Ak (o r A p ) ; th at is, we
m ust form a w ave packet (see Fig. 1-26). T h is w a ve packet can be expressed in the
form
φ(χ) = J A (k )e ikx dk, ( 2.8)

w here A (k ) is the am plitude corresponding to the m om entum p = hk.

Schrodinger’s equation (2.3) describes a particle m ovin g in a straight line (one-
dimensional m otion ). F o r a particle m ovin g in space, the equation becomes

h2 /(bfy I d~Φ 3 2ψ\

E p(x , y, ζ)Φ = Εψ, (2.9)
2 m \c lx 2 QyZ ~! d z 2)

which is the obvious generalization o f E q. (2.3), w ith the three coordinates appear­
ing in a sym m etric w ay. In the case o f a free particle, E p(x , y, z) = 0, and the
equation becomes

_ * 1 ( &2± λ. d2I . =
2 m V f lx 2 dy2 d z 2J ,

T h e solution o f this equation, which describes a free particle m ovin g w ith m om en­
tum p = h k and energy E = h 2 k 2 /2m, is
/
ψ = e
„iit·r

W e leave the verificat ion o f this to the student, who must recall th at

k · r = kxx -f- kyy -I- k2z and kx -j- k 2 -f- A*2 — A2.

E X A M P L E 2.1. Intuitive justification of Schrddinger’s equation.

S o lu tio n : We have said that, in quantum mechanics, the wave function φ (χ ) plays a
role similar to the amplitude f(x ) in a standing wave. For one-dimensional wave motion
the amplitude of a standing wave of wavelength λ satisfies the differential equation,

^ + A2i = O
dx2 + *· ξ U’

where k = 2π/λ is called the wave number of the standing wave. N ow we recall from
Eq. (1.45) that in quantum mechanics p = hk, so that we may expect the wave function
φ (χ ) to satisfy a similar equation of the form
2.4) Polenlial step 59
t
Although when we write the standing-wave equation we assume that k is constant and
that therefore, p should be constant, this is not generally true for a particle subject to a
force. However, we shall use the above equation even when p is not constant. Then,
remembering that the total energy is E = p 2 /2m E ,Ax), we may write

P2 = 2m [E — E pIx)],

and thus the above equation becomes

which, if we make a slight rearrangement of terms, is just Schrodinger’s equation (2.3).

We must emphasize, however, that we have not derived Schrodingcr’s equation, but have
simply, by means of analogy, traced its origin back to the relations (1.44) or (1.45).

2 .1 I tOlvntimI Slvp
A s a first illustration o f the use o f Schrodinger’s equation, let us determ ine the
w ave function ψ (χ ) for a particle m ovin g in a region in which the potential energy
is as illustrated in Fig. 2 -3 ; this situation is called a potential step. T h a t is, the
p otential energy is zero for x < 0 and has the constant value E 0 fo r x > 0. No
physical potential exhibits such an abrupt or sudden change; it is m ore reasonable
to expect the change in potential to be sm ooth, as shown b y the dashed line. F or
example, free electrons in a m etal experience this smooth change o f potential near
the m etal surface. H ow ever, the nonphysical potential step is m athem atically
sim pler and its results are applicable to actual cases, as an indicat ion o f the physical
situation. I t is necessary to consider separately the cases for which E < E 0 and
for which E > E 0.
Ep(x)
E > E0

(I) Ep= E 0

K </io
r
I0
Fig. 2-3. Potential step. (In this and
(II)
all succeeding figures the classically for­
bidden regions are shaded.) k C="
0 X

(a ) E < E 0. In this case, classical mechanics tells us that the particle cannot
be to the righ t o f 0 , because then the kinetic energy E ic = E — E 0 w ould be nega­
tive, which is impossible. Thus x > 0 is a classically forbidden region if E < E 0.
T h is means that, in the case o f free electrons in a metal, those electrons w ith
E < E 0 cannot escape from the m eta l; when th ey reach the surface o f the m etal,
th ey are turned back in to it.
60 Quanlum mechanics (2.4

T o obtain ψ (χ ) for a poten tial step w e m ust w rite Schrodinger’s equation sepa­
rately for the regions x < 0 (o r I ) and :c > 0 (o r I I ) . In region ( I ) , in which
Ep = 0, E q. (2 .3) becomes

d\ I 2m E _
~dx* P -

which is identical to E q. (2.4) for a free particle. Its general solution is o f the ty p e
given in E q. (2.7), or

<Ιί ( χ ) = A e ikx + B e - * * . (2.10)

In the w ay it, is w ritten it represents an incident particle (e 'kz) and a reflected

particle (e~ 'kx). W e are assigning a different am plitude to the reflected particle to
take into account an y possible change o f the incident beam as a result o f the
reflection at x = 0. In region ( I I ) , in which E p{x ) = E 0, Schrodinger’s equation is

^ + = 0· , (2 .11)

W hen E < E 0, we m ay define the p ositive qu a n tity a 2 = 2 m (E 0 — E )/ h 2, so

th at the differential equation ( 2.11) becomes

dV 2 2, n

T h e solution o f this differential equation is a com bination o f the functions eax

and e ~ ax, as w e m ay v e rify b y direct substitution. B u t the increasing function
eax is not acceptable because w e know th at the field am plitude is v e ry small in
region ( I I ) ; experience tells us th at w e are not lik ely to find a p article m that region
(recall our statem ent that, classically speaking, it is im possible). T h erefo re w e
must use on ly the decreasing exponential function e ~ ax, or

M x) = C e~ax.

T h e fact that ψ ι(χ ) is not zero means that there is some p rob a b ility o f finding the
particle in region ( I I ) . T h is constitutes one o f the most interesting pecularities
that distinguish quantum from classical mechanics. T h a t is, in quantum mechan­
ics, the region in which a particle m ay m ove does not, in general, have sharp
boundaries. H ow ever, since ψ (χ ) is given b y a negative (o r decreasing) exponential,
the p robability o f finding the p article w ith E < E 0 to the righ t o f the potential
step (th at is, where x > 0), decreases v e ry rapidly as x increases. In general, there­
fore, the particle cannot go v e ry far into the classically forbidden region.
W e can determ ine the constants A , B , and C on ly by ap p lyin g the condition o f
con tinuity o f the m atter field or w a ve function at x = 0 , which is an obvious
physical requirement. T h a t is, the w a ve function must change sm oothly as it
2.4) j Potential step 61

crosses the potential step. T h is requires th at

and _ ψ for z = 0 .
Ίί = ^2
ax ax

These conditions yield A + B = C and ik (A — B ) = — aC, which in turn g iv e

(ik + a ) /I 2 ik A
B = and C = -
ik — a ik — a
so that

*■(*> = -1 ( * * + § ΐ | * '" * )'

In the form w e have w ritten ^ ll the intensity o f the incoming field is \A\2. T h e
intensity o f the reflected field is

ik + ik + ο: — ik of
\B\2 = μ ι2 = μ ι 2.
ik ik — a — ik — a

T h erefore both the incident and the reflected fields have the same intensity.
W e m ay interpret this result b y saying th at all particles reaching the potential
step w ith E < E 0 bounce back, including those th at penetrate sligh tly into
region ( I I ) . T h is interpretation is in agreem ent w ith the ph3'sical picture o f the
process.
T h e function (x ) can also be w ritten in the alternate form

Ψι ( χ ) = — i(ik ~ oc)eikl + (ik + a )e ~ ikz]

IKe — a

and, rem em bering th at e±,kz = cos kx ± i sin kx, w e obtain a fte r m ultiplication,

Mx) = A (coskx~ l sin*»)'

Thus, disregarding the com mon com plex factor 2ik / (ik — a ) which m ultiplies
Ψι and ψ2, w e can represent both functions b y the curves o f F ig. 2-4. T h e larger
the poten tial energy E 0t the larger the valu e o f a and the faster the function ψ 2
goes to zero fo r x > 0 fo r a given energy E . In the lim it as E 0 becomes v e ry large,

.4

\ /
— .Y
\ \ / 0

F ig. 2-4. W ave function for a potential step of height E 0, when the particle’s energy
E is smaller than E 0.
62 Quantum mechanics (2//

so that a is also v e ry large, the function ^ 2 is essentially identical to zero ( ^ 2 = 0),

and no particle can penetrate into the classically forbidden region at the right
( x > 0). In other words, all particles are reflected a t x = 0. In this case, the ab ove
expression for ψι becomes

Ψι = 2iA sin kx = C sin kx,

as indicated in Fig. 2-5. (T h e student should com pare this situation w ith th at o f
w aves on a string w ith a fixed end.)

F ig. 2-5. (a) Potential wall. The par­

ticle cannot penetrate the region x > 0 .
(b ) W ave function for a potential wall.

(b ) E > E 0. I n this case, if we again assume th at the particles com e from the
left, the classical description would be th at all particles proceed into region ( I I ) ,
although th ey m ove with a sm aller v elocity than in region ( I ) . A t x = 0 the p arti­
cles suffer a sudden deceleration, since th eir kinetic energy is Smaller in ( I I ) than
in ( I ) . T h e quantum-mechanical picture is different. T h e solution fo r region ( I )
is still given b y E q. (2.10), ψ\ = A e lkz + B e ~ ,kz, if w e assume th at it is possible
th at some particles are reflected (an assumption which we shall v e rify later). H o w ­
ever, fo r region ( I I ) the solution is different, because now E > E 0 and we must
define the positive qu an tity k ' 2 = 2m (E — E 0 )/ fi 2 so th a t E q. (2.11) becomes

c^ 2i-'2 1 n
l ^ + k = 0·

T h e solution is now also sim ilar to the solution o f E q. (2.7). One thing is certain
in this case: in region ( I I ) w e have particles travelin g on ly to the right, and thus
w e must w rite

M x ) = Ceik’z. ( 2 . 12)
 Particle in a potential box 63

A p p ly in g the boundary conditions a t x = 0 to the functions given b y Eqs. (2.10)

and ( 2.12), w e then have

A + B = C, k (A - B ) = k’C,

whose solutions arc B = (k — k ')A / (k - f k ') and C = 2 k A / (k + k '), so that

T h e fact th at B is not zero is an indication that some particles are reflected a t

x = 0 , w hicli again is a result d ifferent from that predicted by classical mechanics.
T h is reflection is a characteristic beh avior o f all fields whenever, in th eir propaga­
tion, they encounter a region o f discontinuity in the physical properties o f the
m edium . T h is behavior is w ell known for the case o f elastic and electrom agnetic
waves.

E X A M P L E 2.2. Determine the reflection and the transmission coefficients of the

potential step for E > Eo-

S o lu tio n : Let us call i' - p/m = fik/m the velocity of the particle in region (I ) and
ν' = hk'/m the velocity in region (I I ) . Recall that, the intensity of the incoming particles
(that is, the number of particles per unit volume in the incident beam) is given by |.4|2.
Then the “flux” of the incoming beam or particle current density (that is, the number of
particles passing through a unit area per unit time) is t'|.'l|2. The “ flux” of the reflected
field is i'|S|2, since the speed remains the same for the reflected field, and that of the
transmitted field is t>'|C|2. Thus the reflection and transmission coefficients are

e'|C|2 _ ^ / 2k y _ Akkj
t»|.412 k \ k + k 'J ( k + k' ) 2

Both R and T are smaller than I, since the incoming beam of particles is split into reflected
and transmitted beams. The student should verify that R 4- T = I, which is required for
conservation of the number of particles, since the incoming flux of particles must be
equal to the sum of those reflected and those transmitted.

Si.Λ I tUrtivIp in a I tOiPntiaI Ilo x

Consider, as a second example, the case o f a p article constrained to m ove in the
region from x = 0 to x = a, such as a gas m olecule in a box. T h e m olecule m oves
freely until it hits the w all, which forces the m olecule to bounce back. A sim ilar
situation exists fo r a free electron in a piece o f m etal, if w e neglect th e electron’s
interactions w ith the p ositive ions and if the height o f the poten tial barrier is much
larger than the electron’s kinetic energy. T h e electron can m ove freely through
the m etal but cannot escape from it.
64 Quantum mechanics (2.5

W e m ay represent each o f these physical situations b y the rectangular poten tial

o f F ig. 2-6, which, like the diagram o f the potential energy in Fig. 2-3, is an o v e r­
sim plification o f the poten tial energies th at actu ally occur in nature. T h is sim ­
plified potential energy diagram is called a potential box. W e have Λ’ρ(χ ) = 0 for
0 < x < a, since the particle m oves freely in that region. B u t the potential
energy increases sharply to in fin ity a t x = 0 and x = a. T h is means th at v e ry
strong forces act on the particle at those tw o points, forcing the particle to reverse
its m otion. Then, no m atter what th e valu e o f the energy E , the particle cannot be
to the le ft o f x = 0 or to the right o f x — a. (R em em b er Fig. 2-5 and the dis­
cussion in Section 2.4 concerning v e ry large I i 0.) T herefore, in those tw o regions
(x < 0 and x > a), the w ave function is id entically zero; that is, ψ (χ ) = 0. In
the region 0 < x < a, the problem is essentially that o f a free particle. Schrodin­
g er’s equation for the w a ve function o f a free particle is E q. (2.5). T h a t is

+ k2i = 0, A2 = 2 m E /h 2.

Since the particle is m ovin g back and forth between x = 0 and x = a, the w a ve
function (as in the case o f the potential step ) is g iv e n b y E q. (2.7). T h a t is,

ψ (χ ) = A e ikz + B e ~ ikz,

which contains m otion in both directions. T h e boundary conditions require th at

ψ (χ ) = 0 a t x = 0 and x = a. T h e n ψ (χ = 0) = Λ + B = 0 or B = — A . So

ψ (χ ) = A (e 'kz - e ~ tkz) - 2i A sin kx = C sin kx,

where C = 2 iA . T h e b o u n d a r y c o n d itio n a tx = a gives ψ (χ = o) = C s in ka = 0.

Since C cannot be zero because w e would then have no w a ve function, we conclude
th at sin ka = 0 or ka = me, where n is an integer. Solvin g for k, w e have

k = nic I a or p = hk = n xti/a, (2.13)

which gives the possible values o f the m om entum p = hk o f the particle.*

T h e energy o f the particle corresponding to the Axvalues given b y E q. (2.13) is

2 j 2; 2 2 2* 2
Ε = ξ - = ^ = (2.14)
2m 2 m 2 m a2

* The student may now recognize the extraordinary similarity between the mathematical
methods used in several different physical problems, such as the vibrating string with
fixed ends and the present problem of a particle in a potential box. The physical situation
changes, but the mathematical technique remains the same. (This is why it is so important
to master some basic mathematics before undertaking the study of physics.) W e must
warn the student, however, against thinking that, because the mathematical formalism
is the same, the physical situations are similar. He must not think, for example, that
matter waves are similar to waves along a string.
 Particle in a potential box 65

Kl = U i f l
h =4-

Ka = Df I
n = 3-

Ki = 4 f I
ii = 2 -

Ki =Iii TiZimdi
It=I-

F ig. 2-6. One-dimensional potential F ig. 2-7. Energy levels Ior a one-
box of width a . dimensional potential box.

or, if E i = h 2 w 2 /‘2 iiia 2 is the energy fo r n = I, then E = E u 4 E U O E 1, . . .

W e conclude then that the particle cannot h a ve any arb itrary energy, but on ly
those values g iven b y E q . (2.14) and shown in Fig. 2 -7 ; that is, the en ergy o f the
particle is quantized. T h is is a new situation, since in the previous exam ple o f the
potential step we did n ot have to im pose an y lim itations on the energy.
T h is situation o f on ly certain energy values being allow ed is n ot a pecu liarity
o f this particular problem , but it gen erally holds w h enever Schrodinger’s equa­
tion ( 2.3) is solved for a potential energy which confines th e particle to m ove in a
lim ited region. (R e ca ll th at in the case o f the poten tial step the particle is not
confined to a lim ited region and thus the energy is not qu antized .) E n e rgy quan­
tization is due to the fact, th at the w a ve function is determ ined by the poten tial
energy and the boundary conditions. A n acceptable w a v e function Ψ (χ), satisfyin g
the boundary conditions o f the physical problem , in general exists on ly fo r certain
values E i 1 E 2, E 3 , . . . , E n, . . . o f the energy. T h erefo re th e m athem atical form al­
ism o f quantum mechanics, as expressed b y Schrodinger’s equation, incorporates
the quantization o f energy and the existence o f a discrete set o f allow ed energy
levels in a natural way. In this problem we are considering, w e find that, in ad d i­
tion to the fact th at the energy o f the particle is quantized, the m om entum o f the
particle is quantized also, with possible values given b y E q. (2.13). This, however,
is not the general ease.
T h e w a v e functions corresponding to the Ic values g iven by E q. (2.13) arc

Φ „(χ ) — C s in ( « 7Γ.ι·/α), ( 2. Ιό )

which, in fact, arc identical w ith the allowed am plitude functions for standing w aves
in a vib ra tin g string w ith fixed ends. T h e w a ve functions for the first three energy
66 Quantum mechanics (2.5

I .me of symmetry l.ine of symmetry

.r = 0
(«) (l>)

F ig. 2-8. (a) First three wave functions for a particle in a potential box. (b ) Corre­
sponding probability densities.

levels arc represented in F ig. 2 -8 (a ). In F ig . 2 -8 (b ) th e prob ab ility density \ψη \2

has been indicated for the same energy levels.

In cid en tally, in this sim ple case w e could have d erived the energy values given
in Erp (2.14) by using the an alogy w ith the vib ra tin g string. T h e student m ay
recall that in order to have standing w aves in a string w ith fixed ends a distance a
apart, the w avelength λ must have the values

iX = a, la , la , . . . , ^ a X = 2
-^ .
Tl

Then p = A/X = nh/'2a = ηπίι/α are the possible values o f the m om entum , in
agreem ent w ith Etp (2 .13 ); th erefore the energy is given b y E q. (2.14). H o w ever,
for m ore com plex potentials, this an alogy does n ot ap p ly, and a solution o f Schrb-
dinger’s equation is required.
I t is interesting to note that th e m inim um energy o f a particle in a potential box
is E 1 = : b n 2 /2ma 2 and n ot zero, as one would suspect. T h is m inim um energy is
related to the uncertainty principle. T h e uncertainty in the position o f the particle
is, obviou sly, A x ~ a. T h e p article is m o v in g back and forth w ith a m om entum p;
the uncertainty in the m om entum is then A p ~ 2p. T h e uncertainty principle
2.5) Parlicle in a potential box 67

requires th at Ax Ap > A. T lie re fo re a (2 p ) > Ii or p > π)ι/α, g ivin g E > E\. T h e

existence o f a zero-point energy, as E i is som etim es called, is typical o f all problem s
in which a particle is confined to m ove in a lim ited region.
T o com plete our discussion, w e shall determ ine the constant C which appears in
E q. (2.15). T h e norm alization condition (2.21) in this case is

because the range o f the function is from O to a. T h e value o f the integral is ία .

Thus C 2( i a ) = I or C — \/2/a. T h erefo re the norm alized w ave functions are

Φ η(χ) = V 2/ o s in ( n iri/ a ).

A n oth er interesting p rop erty o f w a v e functions is th at th ey are orthogonal; that

is,
(2.16)

W e m a y v e rify this in the present case as follow s: N o tin g that the functions φ „(x )
are real and thus φ * (χ ) = Φη (.c), w e m ay w rite

n — i i ') π χ
— cos
a

w here w e have used the trigonom etric iden tities for cos (a ± 0 ).
I t can be shown th at the prop erty o f o rth ogon a lity is a general p rop erty o f the
solutions o f Schrodinger’s equation and not a pecu liarity o f the potential-box func-
tions (see Section 2.12).

E X A M P L E 2.3. Obtain the energy levels and wave functions for a particle inside a
potential box of sides a, b, and c (Fig. 2-9).
X

F ig. 2-9. Three-dimensional potential box.

.V
68 Quantum mechanics (2.5

S o lu tio n : Extending our previous reasoning, we note that the three components px, p„,
and pj of the momentum of the particle must satisfy relations similar to Eq. (2.13) for a
one-dimensional box. Thus

ichn\ Tchn2 Tchn3

p - ’ * - — · p' = — ’

where n i, tt2, and »3 are integers. Thus

n I 2 I , 2 , 2 , 2>
E = ^ P = 2^ (p ' + ^ + p ' )
2,2 / 2 2 2\
7Γ /i / n | 712 , W3 1
(2.17)
" f 2/

This expression gives the energy levels of a particle in a three-dimensional potential box.
B y comparing Eq. (2.17) with Eq. (2.15), we find that the wave function can be expressed
by
, _ . iiivrx . U iicu . U3 Tez
φ = C sin------ sm —7— s m (2.18)
a u c

The student should verify, by direct substitution of Eq. (2.18) in Schrodinger’s equa­
tion (2.9),with E p= 0, that the value given by Eq. (2.17) for theenergy also results,
and thatψ = 0 at the six faces of the potential box; this was the samerequirement
imposed for a one-dimensional potential box. N ote also that Eq. (2.18) is formally
identical to the equation for the amplitude function for standing waves trapped in a
rectangular cavity.
An important situation arises when the potential box is cubical; that is, when a = 6 = c.
Then the possible energies are given by

7T~r 2 , 2 , 2, Tth2 2
E = -z— 5 (m + U2 + n3) = r — 7, *
Im a 1 2i « « -

where K2 - n\ -f- U2 n3, and the corresponding wave functions are

, _ . m i x . Tcn2y . icn3z
Ψ = C sm sm sin -------
a n a

N ote that the energy depends only 011 k2 = nf -I- n2 -)- « 3. This means that all states
corresponding to all integers m , n 2, and 113 which give the same value for κ have the
same energy. However, when the numbers ni, « 2 , and n 3 are changed without changing
the value of κ, the wave function also changes. Thus a certain energy level may be asso­
ciated with several wave functions or dynamical states. When this happens, degeneracy
is said to exist. The order of degeneracy of an energy level, designated by g, is equal to the
number of different (or independent) wave functions for the given energy. These are
illustrated for the first six energy levels of a cubical potential box in Table 2-1, where E i
is equal to π2Λ2/2ι»ο 2.

E X A M P L E 2.4. Discuss the number of energy levels in a small energy range dE for
a particle in a very large potential box.
2.5) Particle in a potential box 69

T A B L K 2-1 Energy Levels a n d Degeneracies in a

C u b ica l Box (E i = r 2 h2 /2ma2)

Energy Combinations of n,, « 2, ns Degeneracy, g

3/ί I (I , I, D I
6E 1 ( 2, I, I)(I, 2, 1) ( 1, 1, 2) 3
9E 1 ( 2, 2, I ) ( 2, I, 2) ( 1, 2, 2) 3
I IZil (3, I, I)(I, 3, 1)(1, I, 3) 3
12/i I ( 2, 2, 2) I
14/i, (I , 2, 3)(3, 2, 1)(2, 3, I) 6
(1 ,3 , 2)(2, I, 3)(3, 1,2)

S o lu tio n : Kor simplicity we shall consider a cubical potential box of side a. Then, as
we saw in the previous problem, the energy levels of a particle in the box are given by

2.2
V h , 2 I 2 , 2.
E = - — 5 (n I + Λ2 + n - i) ,
Zma2

where B i, n i, n-i are integers. We note that for a small box (i.e., small value of a) the
energy levels are spaced widely, as shown in Fig. 2 - 10(a). But for a very large box, as
is the case for molecules of a gas in a container or for electrons in a metal, successive levels
are so close that, they practically form a continuous spectrum, as shown in Fig. 2-10(b).

_______UEi

I2Ei
IlK i

()#i

Fig. 2-10. Energy levels for (a) a small -------------------------

potential box, (b ) a large potential box.

E=0

Hmall box (a = 6 = c)

(a)

Our problem is to find how many energy levels there are in a small energy range dE when
the potential box is very large. This problem is very similar to that of Iinding the modes
of oscillations of waves trapped in a cavity whose dimensions are much larger than the
wavelength.
70 Quantum mechanics (2.5

Let us introduce the coordinates £, η, f in a certain representative space (Fig. 2-11);

each point, of coordinates ξ = m , η = « 2, and f = 713, represents an energy level, and
to each point there corresponds a cell of unit volume in this representative space. Let us
define κ2 = £2 + η2 + f 2, and say that the number of points having positive integral
coordinates and lying on the surface of a sphere of radius κ give the different states asso­
ciated with the energy

2,2
TT Il 2
E
2ma2 K

T o find the number of states N (E ) with energy between zero and E 1 we must find the
volume of an octant of a sphere of radius <c, since only positive values of n 1, « 2, and n3
are allowed. Thus, remembering that h = h/2ir, we obtain

N (E ) = i ( W ) = I V ( g g ) 3' 2 = g (2m3) li2E3i2,

where F = a3 is the volume of the potential box. The number of states with energy
between E and E + dE is obtained by differentiating the above expression. This yields

j in n 3 .1 / 2
dJV(E) = 4lrV(2™ ) E 1 1 2 dE.
/i3

I t is convenient to write d N (E ) = g (E ) dE, so that

dN 4wV(2m3 ) 1 1 2 1/2
(2.19)
9 (E )= 7 e W — b

is the number of states per unit energy interval at the energy E. The function g (E ) is
plotted in Fig. 2-12. The area of a strip of width dE gives the corresponding number
d N = g (E ) dE of states in such an energy range. The area under the curve from E = O
to E = i gives the total number of states in that energy interval. W e shall have the
opportunity to use Eq. (2.19) in several problems to appear later in this book.

g(E)

F igu re 2-11 F ig. 2-12. Density of energy levels

in a large cubical potential box.
2.6) The harmonic oscillator 71

In some instances it is more convenient to use the number of states within the momen­
tum interval dp between p and p -f- dp. Recalling that the particle within the box acts
as a free particle, we have E = p'/2m . Defining g{p) so that d.V = g(p ) dp = g (E ) dE,
we have

dN . . .-d E 4nV 2
= m - = — p.

This expression applies as well for the number of modes of longitudinal waves trapped in
a cavity of volume V. In such cases it is more convenient to use the frequency r. We
recall that p = Λ/λ and v = c/\, where c is the phase velocity of the waves. Therefore,
defining g(v) so that g(v) dv = g(p ) dp, we have

dp 4 tV 2
( 2 .20)
SM = H (P )^ = IT "-

which is a very useful relation.

B p(X )

I Ί■

ίΐω

n
I
3 J

j
I
I

(b)

F ig. 2-13. (a) Potential energy of a harmonic oscillator, (b) Energy levels.

li.fi T h v H a rm o n iv O svillafor
A n im portant physical problem is th at o f a harm onic oscillator, fo r which the
potential energy is E p = ^kx2, as shown in F ig. 2-13. T h is problem provides
im portant inform ation about atom ic vib ration s in m olecules and solids since, as a
first approxim ation, w e m ay assume th at the rela tive m otion o f the atom s in m ol­
ecules and solids is a harm onic oscillation. Schrodinger’s equation (2.3) is now
72 Quantum mechanics

W e shall not attem p t to solve this equation in a form al w a y ; rather w e shall £ive
on ly the main results. R em em bering th at for a harmonic oscillator w = y/k/m
is the angular frequency, w e find th at the possible values o f the energy fo r the
stationary states are

En = { n + J)ftw, (2-21)

w here n is zero or a positive integer; that is, n = 0, I, 2, 3, . . . T h u s E n = Jftw,

fftw, fftw, etc. T h e energy levels indicated in Fig. 2-13 are equally spaced b y the
am ount ftw (o r hv, since ft = Α/27Γ and w = 2 π ν ).
A n interesting result is that the m inim um energy o f the harmonic oscillator is
Jftto or ^hv. T h is is called the zero-point energy o f the oscillator because it cor­
responds to n = 0. T h is result, lik e the sim ilar result for the poten tial box, is
closely related to the uncertainty principle. T h e classical m inimum energy cor­
responds to the point 0 a t the bottom o f the potential energy curve. H ow ever, a t
this p oin t w e have x = 0 and also p - 0. Because there would be no oscillations
in such a situation, we would know sim ultaneously and w ith absolute precision
both the position and the m om entum o f the p article; this would con tradict the
uncertainty principle. T h erefore the first energy level or ground state should be
the low est energy level com patible w ith the uncertainty principle. T o see this, w e
note th at fo r this particular level the am plitude X0 o f the oscillations is v e ry small,
and w e can m ake X 0 ~ J Δχ. A lso the am plitude p 0 o f the mom entum change is
v e ry small and w e can m ake Po ~ J Δ ρ . T h e energy o f a classical oscillator o f
am plitude x 0 is E = Jmw2Xo, alicIi noting that p 0 = mwx0, w e have

E = Jwiw2Xo = §<*)(x0)(m w xo) = Jwx0po ~ Jw Δ χ Ap ~ Jftw ~ Jftw.

T h e general expression o f the w a v e functions for the sim ple harm onic oscillator
w ill not be given here (see Problem 2 .1G). T a b le 2 -2 presents the first few w a v e
functions, w ith ψ() corresponding to the ground state. These functions are illus­
trated in Fig. 2-14. Observe th at they do not fall sharply to zero at the classical
lim its o f oscillation, indicated b y the short v ertical line in each case. R a th er they
extend beyond them, although th ey decrease v e ry rapidly, as w e found previously
for a poten tial step in Section 2.4 when E < E 0 (F ig . 2 -4 ). T h is means that the

T A B L E 2-2 W ave F u n etion s o f a H a rm o n ic O scillator

(a 2 = r n W /f t)

» En Φ Λχ)

0 Jftw Ίό ( χ )
I Jftw Ψ ι(χ) = (o/2\/,tr) l/22axf
2 Jftw i i i x ) — (a/’8 v t r ) 1/2(4n2x 2 — 2)c ~ a' x2rl
3 Jftw Ί 'ί(χ ) = (a / 4 S v'tr) l/2(8a3x 3 — 12a i)c ~ ° 2 j 2 / '2
2.6) The harmonic oscillator 73
\

F ig. 2-14. W ave functions correspond- F ig. 2-15. Probability densities corre-
ing to the first four energy levels of a bar- sponding to the first four energy levels of
monic oscillator. a harmonic oscillator.

am plitude o f an oscillator is not sharply defined in quantum mechanics, as it is

in the classical case. In quantum mechanics the particle m ay be found a t a particu­
lar instant in a region in which, in the m ore rigid formalism o f classical mechanics,
its m otion is considered to be impossible. T h e re are, however, m any experim ent?
supporting this conclusion. (W e shall discuss them later on.) T h e prob ab ility
density P = |^(.r)|2 is indicated in F ig. 2-15 for the states corresponding to the
w ave functions shown in F ig. 2-14. N o te that, although the p rob a b ility o f ob ­
serving the particle outside the classical lim its o f oscillation is finite, th e p article
is m a in ly confined to the classical region.
So far w e have discussed a linear oscillator; th at is, an oscillator in only one
dimension. In the general case o f three dimensions, such as the case o f an atom in
a solid, the energy levels are g iven by

En = (n + 3 )fc »· ( 2.22)

T h e on ly difference is th at now the zero-point energy is §Λω instead o f 4Λω, be­

cause w e m ust add the zero-point energies fo r oscillations along the X - , Y -, and Z -
axes, corresponding to an energy o f i /ιω for each coordinate.

E X A M P L E 2.5. Discuss the possible stationary states for the potential energy illus­
trated in Fig. 2-16, which is called a potential well. This potential energy is defined by
E p = — Eo for |x| < a/2 and = 0 for |r| > a/2. A potential energy of this form has
many important applications, especially when one is dealing with the so-called finite-
range forces; i.e., forces that are negligible at distances greater than a certain value called
the range, meaning that the potential is constant outside the range. This situation seems
to be applicable to the nuclear forces.
74 QuarUum mechanics (2.6

-a / 2 ψ (χ ) a/2

E = E3

F ig. 2-16. One-dimensional rectangular

potential well of width a and depth E o.

F ig. 2-17. First three wave functions

in a one-dimensional potential well.

S o lu tio n : This problem is equivalent to having two mirror-image potential steps sepa­
rated the distance a. Classically speaking, for a negative energy E (that is, E < 0) the
particle should be confined within the well; that is, the particle should remain between
x = —a/2 and x = +a/2 . However, from our previous examples we suspect that in
quantum mechanics this is not the case. For region (I ), in which —a/2 < x < a/2, the
potential energy is constant and the particle is essentially free, although constrained to
move back and forth. Thus its field amplitude ψ ι(χ ) must again be a harmonic function
of type (2.7). In the forbidden regions ( I I ) and ( I I I ) , the field amplitudes <p2 (x ) and
Φ'λ(χ) must decay exponentially, as previously indicated in Fig. 2-4 for a single potential
step. Therefore the boundary condition used to obtain the wave function of Fig. 2-4
must be applied twice, once at x = —a/2 and once at x = a/2. Because we are imposing
two sets of boundary conditions, they can be satisfied only for certain values of the energy.
Thus the energy E of a particle in a potential well is quantized. The possible values of
E cannot be expressed in a closed form and will not be given here (sec Example 2.6 for a
similar case). The number of energy levels is limited, being only one, or two, or three,
etc., depending on the depth Eo and the range a of the potential. That is, for the case in
which E o a 2 < Tr2fi2/2m, there is only one possible energy level; for

■π2K2/2m < E oa 2 < Air2Ii2/2m,

there are two energy levels; for

Air2h2/2m < E oa 2 < Htt2 Ii2 /2m,

there are three, and so on.

2.7) Energy levels and wave functions in general 75

The wave functions for the ground state and the first two excited states are shown in
Fig. 2-17 for the case in which three energy levels are allowed. Note the similarity to
the wave functions for the harmonic oscillator. The student should plot the probability
density Ij = \f \2 corresponding to these states; we also leave the student to think about
the situation when E > Eu, and to sketch the wave functions and probability densities.
In this case, all energy values are acceptable and the energy is not quantized.

S. 7 Envrfifi L v rv ls a nd W n r v F u n vlion s in E vn vrn l

T lie discussion o f the poten tial step, the potential box, the harm onic oscillator,
and the poten tial well suggest the general nature o f the stationary states and w a v e
functions. F igu re 2 -1 8 (a ) shows a potential energy E p( x ) sim ilar to th at found in
a central force problem or in a diatom ic molecule. A t large x the potential energy
becomes essentially constant a t a value chosen as the zero o f energy, which is the
m ost usual convention. T h e potential energy decreases as the distance decreases,
ind icaiin g an a ttra c tiv e force. A t M the potential energy is a m inim um, and is
equal to — Eg·, the corresponding distance r 0 from 0 is the classical equilibrium
separation. A s the distance decreases further, the poten tial energy increases
rapidly, indicating a repulsive force.
F o r n egative energies the m otion is classically bounded. F or exam ple, when
the particle has an energy E , the classical m otion is oscillatory betw een A and B .
T hese tw o points are called the classical lim ils o f oscillation. F o r p ositive energies
( E > 0) such as E ', a particle com ing from the right is stopped when it reaches C
and bounces back, receding to infinity. T h is is w hy C is called the classical turn in g
point.

Energy
continuum

Ei
Es

Es

Ei

(a) (b)

F ig . 2-18. (a) General potential energy curve corresponding to strong repulsion at

small values of x and negligible interaction at large values of x. (b) Energy levels cor­
responding to the potential energy shown in (a).
76' Quantum mechanics (2.7

In quantum mechanics the description is basically th e same, but certain new

features appear: (a ) T h e bound states occur on ly fo r certain negative energies, so
th at for E < 0 there is a discrete spectrum o f en ergy levels or states. T h is is true be­
cause, for E < 0, the m otion is lim ited a t both classical lim its o f oscillation, thus
im posing two boundary conditions on the w a v e functions. H ence appropriate
solutions o f Schrodinger’s equation exist on ly for certain energies. T h is is the same
situation w e found, for exam ple, in the case o f the potential box. (b ) Unbound
states exist for all positive energies; w e then say that, for E > 0, there is a con­
tinuous spectrum o f energy levels or states. T h e reason for this is that, when E > 0,
the m otion is lim ited at only one point, the classical turning point so that on ly one
boundary condition is required. Enough fle x ib ility is then le ft to allow a solution
o f Schrodinger’s equation w ith one arb itra ry constant: the energy. T h is situation
has already arisen in the case o f the poten tial step. Ph ysically, the situation arises
because w e can alw ays arb itrarily fix the energy o f the particle when it is a t a
great distance, as w e do, for exam ple, when a charged particle is accelerated in a
m achine anti thrown against a target nucleus; or when one atom collides w ith
another in a gas. (T h e discrete and continuous energy spectra are shown schem at­
ically in F ig. 2-1 8b .) H ow ever, in the case o f a potential energy such as that
shown in F ig. 2-13, corresponding to the harm onic oscillator, there is no con tin­
uous energy spectrum and all levels are discrete.
W hen the particle is in a bound state o f n egative energy E , the m inim um
energy that m ust be supplied to the particle to rem ove it to a v e ry large distance
is E b = — E . T h is is called the binding energy o f the particle in that state. (Som e­
times, when w e are referring to the ground state o f a d iatom ic m olecule, w e call it
the dissociation energy, because it is the m inimum energy required to separate the
tw o atom s when the m olecule is in the ground state. In the case o f an electron in
an atom o r m olecule, w e also call it the ionization energy.)
F o r E < 0, the w a v e functions resemble those o f the harmonic oscillator, except
th a t th eir exact shape depends on the form o f the potential energy E „ (x ). F ig ­
ure 2-19 shows the w a v e function for a n egative energy level ( E < 0) o f the dis­
crete spectrum (a bound state) and the w a ve function for a positive energy level
( E > 0) o f the continuous spectrum (an unbound state). In both cases the w a ve
functions extend beyond the classical lim its o f m otion, b u t decrease v e ry rap idly
outside those lim its. In particular, for large x, the w a v e function o f a p ositive
energy or unbound state resembles th at o f a free p article and has the asym p totic
form given b y E q. (2.7),

φ (χ ) A e ikx + B e - * 1,

since it must represent both the incom ing particle and the ou tgoing or reflected
particle.

E X A M P L E 2.6. Discuss the energy levels and wave functions for the potential energy
described by the curve shown in Fig. 2-20. A t x = 0 the potential energy goes to infinity.
For 0 < x < a, the potential energy has the constant value E = — Eo and for x > a
it is zero. Thus it is a “square” idealization of the potential-energy curve of Fig. 2-18.
2.7) Energy levels and wave functions in general 77

F ig. 2-19. Shape of wave functions for F ig. 2-20. Rectangular potential well
bound and unbound states corresponding limited at x = 0 by a potential wall,
to the potential energy shown in Fig. 2-18(a).

S o lu tio n : First consider the case when E < 0, which corresponds to bound states. In
such a case the particle is forced to move classically in the region between x = 0 and
x = a, or region (I ). The energy Eb = — E is then the dissociation or binding energy;
i.e., the minimum energy required to remove the particle from the potential well. Schro­
dinger’s equation (2.3) for that region, since E p(x ) = — Eo, becomes

- a ® - * * - * “ e M * - » ·

where k f = 2m{Eo + E)/h 2 = 2m (E 0 — £»)/ft2, and p, = N a is the momentum inside

the well. The solution of this equation is given by Eq. (2.7) or

φ I {x) = .le 1*·1 + B e~'k‘r.

Remembering the case of the potential box, we must require that ψι = 0 at x = 0; this
means that .4 + B = 0 or B = — .I. "'hus

(x) = A ie i k ' 1 — e~iki‘ ) = C sin lax,

where C = 2 t.l. In region ( I I ) , corresponding to x > a, Schrddinger’s equation with

Ep(x) = 0 becomes

r dV „. dV 2 . ..
— 2m dx2 = °r d ^ - ^ = 0’
where
a2 = -Im E Ih 2 = ImEb/h2.
78 Quantum mechanics (2.7

When we recall the discussion of the potential step in Section 2.4, we see that the solution
of this equation is

Ψ ί(χ) = De- " .

N ext we must satisfy the continuity conditions of the wave function at x = a; that is,

^ t = Ψ2 and (/ψι/dx = d^/dx.

T hey yield
CsinAqa — De-00 and AqCcosAqa = —a D e ~ °a.

Dividing these two equations to eliminate the constants C and D, we obtain

Aq cot Aqa = —a (2.23)

or, introducing the expressions for Aq and a, we have

[2m(Co - Ε ύ /h] 1' 2 cot [2m(A?o - & )/ A l1/2a = - [ 2 mEb/H]'12.

In this equation the only quantity that has been left arbitrary so far is the energy Eby
Thus it expresses a condition for the possible energy levels inside the well. However, since
it is a transcendental equation, it is difficult to obtain Eb in a closed form, as we did for
the potential box. The situation is very similar to that described before in connection
with the square well (Example 2.5). Thus, depending on the depth Eo of the well, there
may be none, one, two, etc., possible energy levels. I t can be verified that if

E o a 2 < π 2ft2/Sm ,

there is no bound state; if

■K2 h 2 /8 m < Eoa 2 < Qn2H2/ 8m ,

there is only one bound state; if

Qtc2H2/Sm < Eoa 2 < 25r2fti /8m,

there are two bound states, and so on.

Thus the number of bound energy levels
depends on the value of the product Eoa 2
or energy X (range)2.

F ig. 2-21. W ave functions correspond­

ing to the potential well shown in Fig. 2-20.
2.7) Energy levels and wave functions in general 79

The wave functions for the case in which there are three bound states are shown in
Fig. 2-21. The student should compare these wave functions with those given for the
potential energy illustrated in Fig. 2-18. Thus this relatively simple example may help
him to better understand our discussion in connection with the more physical potential
enelgy of Fig. 2-18.
Next let us consider the positive energy states (that is, when E > 0). VVe note that
they do not correspond to bound states, since a particle may now move between x = 0
and i = oo. Again using k f = 2m(Eo + E)/h2, so that p, = hki is the momentum in­
side the well, we may write the solution for x < a as before; that is,

φ\(χ) = C sin kiX.

For x > a, where E p — 0, Schrodinger's equation is now

h~ drf/ ά 'φ 2. n
2m djfi ~ °Γ d ^ + * * = 0-

where k2 = 2m E / fr and p — hk is the free particle momentum outside the well. The
solution to this equation is of the type given by Eq. (2.7). However, in this case it is more
convenient to write it in the equivalent form*

ψ ί(χ ) = O sin (At + 6).

The quantity δ is called the phase shift; its physical meaning will be explained shortly.
Applying the continuity conditions of the wave function at x = a, we obtain

ki cot k,a = k cot (ka 4- 5). (2.24)

This equation differs from Eq. (2.23) in that it contains, among other things, an arbitrary
quantity 5, the phase shift. Thus we can always satisfy Eq. (2.24) for any energy E (or
momentum hk) by properly choosing the phase shift 5; therefore the positive energy
spectrum is continuous, as expected.
We can understand the origin of the phase shift in the following manner. I f the poten­
tial energy were of the type considered in Fig. 2-5, and shown (reversed) in Fig. 2-22(a),
the wave function would have been ψ ~ sin kx ~ e'kx — e ~ 'kx which contains the incident
and reflected beams of particles, both having a wavelength λ = 2ir/k. But when we in­
troduce the potential well (Fig. 2-22b), the wave function is distorted in the region
0 < x < a, and, although the wavelength at z > a is still 2ir/k, the curve sin kx must
be moved along the -Y-axis the distance δ/k so that it smoothly joins with the wave func­
tion inside the well at x = a (which has a different wavelength λ, = 2π/kf). In other
words, a local modification of the potential energy between x = 0 and x = a affects the
whole wave function. This is expressed by a phase shift δ for x > a.

* W e may see that the two forms are equivalent if we recall that

Ciik l — cos kx ± i sin kx.

Then
<// = Aeikl + B e~ik* = (.4 -f- B ) cos kx + * ( -T — B) sin kx
= C sin (kx Ar δ),

where tan δ = (.-I + B )/ i(A —B ).

80 Quantum mechanics ( 2.8

Ep Ep

In cident In ciden t
Reflected
Reflected

a
O
T

E0

F ig. 2-22. Origin of the phase shift.

h p( x )
I
I

In cident particles
L·0

I
T ra n sm itted particles
R eflected particles

O
W j - I U j - mij ·

F ig. 2-23. Rectangular potential barrier of width a and height Eo-

2.11 V o tv n tia l H a rrier I tVnetration

T h e fact that a w ave function m ay extend beyond th e classical lim its o f m otion
gives rise to an im portant phenomenon called potential barrier penetration. Let
us consider the potential represented in F ig. 2-23. I t consists o f tw o poten tial
steps, but in the reverse order o f the potential w e ll o f Fig. 2-16. I t is called a
potential barrier. A s before, w e shall consider the cases E < E 0 and E > E 0
separately. Classical mechanics requires th at a p article com ing from the le ft w ith
2.8) Potential barrier penetration 81

*(x)

F ig. 2-24. W ave function corresponding to the potential barrier of Fig. 2-23 for an
energy less than the height of the barrier.

an energy E < E 0 should be reflected back a t x = 0, as discussed before in Sec­

tion 2.4. H o w ever, when w e consider the problem according to quantum mechanics
b y obtaining the solution o f Schrodinger’s equation for regions ( I ) , ( I I ) , and ( I I I ) ,
w e find th at the w ave function has, in general, th e form illustrated in Fig. 2-24.
Its com ponents are o f the form

ψι = A e ikx + B e ~ ikz, φ2 = Ceax + D e ~ ax, φ3 = A 'e ikx,

where k and a arc the same as in Section 2.4; th at is, k 2 = 2m E /h 2 and a 2 —

2 m (E 0 — E )/ h 2. T h e w a v e function ψχ, as in previous cases, contains the inci­
dent and the reflected particles; ψ2 decays exponentially, but it must also contain
the p ositive exponential, since the barrier extends on ly up to x — a and the posi­
tiv e exponential is not necessarily to be excluded, as it was in the case o f the
potential step. Because f 2 is not y e t zero a t x = a, the w a ve function continues
into region ( I I I ) w ith the oscillating form ψ2, which represents the transm itted
particles which have the same energy as the incident, particles, but an am plitude
A ' which, in general, is different from A . Since ψ 3 is not zero, there is a finite
p rob a b ility o f finding the particle in region ( I I I ) . In other words, it is possible f o r
a particle to go through the potential barrier even i f Hs kinetic energy is less than the
height o f the potential barrier.
W h en E > E 0, the classical description o f th e process indicates that all particles
should cross the poten tial barrier and reach the right-hand side. H ow ever, in
quantum mechanics, for the same reason as in th e case o f the potential step, som e
particles are reflected a t x = 0 and a t x = a. H ence the w a ve functions in the
three regions are now

ψι = A e ikx + B e ~ ikz, φ2 = Ceik'x + D e ^ 'f , φ3 = A 'e ikx,

w here k ' 2 = 2m (E — E 0 )/ h 2 and hk' is the m om entum o f the particles while they
are crossing the poten tial barrier.
82 Quantum mechanics (.2.8

E/Eo

F ig. 2-25. Transmission coefficient of a rectangular potential barrier.

I

B y ap p lyin g the boundary conditions a t x = 0 and x = a, we can determ ine the

coefficients B 1 C , D , and A ' in terms o f A both in the case o f E < E 0 and in the
case o f E > E 0. T h e transparency o f the barrier is defined as T = \A'\2/\A\2.
I t varies w ith the energy E , as shown in Fig. 2-25. N o te th at for E > E 0 theref is
p erfect transmission (T = I ) for certain values o f E f E 0 which correspond to a
w avelen gth o f the particle while it is crossing the potential barrier given b y λ ' =
'2ic/k\ which is equal to a m ultiple o f 2a. T h is is considered a resonance effect.
F igu re 2-26 illustrates a m ore general case. A ccord in g to classical mechanics,
if the p article has an energy E it m ay m ove between A and B or between C and D .
I f the particle was in itia lly between A and B it w ill never be found between C and
D , and conversely. B u t again in quantum mechanics the logic is different. W hen
w e solve Schrodinger’s equation for this potential, w e obtain a w a v e function φ,

F ig. 2-26. General case of a potential barrier.

2.8) Potential barrier penetration 83

F ig. 2-27. Shape of the wave function in the general ease of a potential barrier.

as shown in F ig. 2-27. W e expect, front our previous examples, th at between A

and B the w a ve function w ill be oscillatory, but to the right o f /f it, must v a ry
exponentially. H o w ev e r at C the w a v e function still has a finite value. B etw een
C and D , which is a classically allowed region, the w a ve function becomes oscilla­
to ry again. T o the righ t o f I ) the w a ve function decreases once m ore exponentially.
T h erefo re w e conclude th at there is a finite p rob ab ility that the particle will be
found either between A and B or between C and D . In other words, if the p article
is in itially between A and B, a t a later tim e it m ay be between C and D , and con­
versely. F o r this to happen, the p article m ust penetrate the potential barrier be­
tween B and C.
P en etration o f a poten tial barrier has no analog in classical mechanics because
it corresponds to a situation in w hich a particle has a negative kinetic energy or an
im agin ary m om entum . T h is should not present any difficulty in quantum m echan­
ics, how ever, since w e m ust n ot insist on using the logic o f classical mechanics in
the atom ic dom ain. B arrier penetration has been observed in m any situations, o f
which w e shall discuss two.
T h e m olecule o f am monia, N H 3, is a pyram id w ith the N atom a t the v e rte x
and the three H atom s at the base, as shown in F ig. 2 -2 8 (a ). O bviou sly the N

F ig. 2-28. (a) Inversion motion of the nitrogen atom in the ammonia molecule, (b)
Potential energy for the inversion motion.
84 Quantum mechanics (2.8

F ig. 2-29. (a) Potential energy for an electron in a metal with no external electric
field, (b) Resultant potential energy when an external electric field is applied.

atom m ay be at one o f the tw o sym m etric equilibrium positions N and N ' on either
side o f the base o f the pyram id. Since both N and N ' must be equilibrium posi­
tions, the potential energy for the m otion o f the N atom along the axis o f the
pyram id must have tw o m inim a and have the sym m etric shape indicated in
F ig. 2 -2 8 (b ), w ith a potential barrier between N and N '. I f the N atom is initially
a t N , it m ay even tually leak through the potential barrier and appear a t N '. If
the energy o f this m otion is less than the height o f the potential barrier, such as
th e energy level E in the figure, the m otion o f the N atom is composed o f an oscil­
lato ry m otion between R and S or between T and U , depending on which side o f
the plane it happens to be, plus a much slower oscillatory m otion between the tw o
classical regions passing through the potential barrier. T h e frequency o f this second
m otion is 2.3786 X IO 10 I I z for the ground state o f X H 3. I t is this second ty p e o f
m otion which w e use to define a tim e standard w ith atom ic clocks.
A s another example, let us consider the case o f the electrons in a m etal. T h e ir
poten tial energy is shown in F ig. 2 -2 9 (a ). I f an electron at the highest energy level
is to escape from the metal, an am ount o f energy at least equal to φη must be sup­
plied to the electron. T h is am ount o f energy m ay be provided b y heating the m etal
or b y the absorption o f a photon (as in the photoelectric effect). B ut the electron
m a y also escape if one applies an external electric field whose potential is shown by
the dashed straight line in Fig. 2 -2 9 (b ). T h e resultant poten tial energy is illus­
trated by the solid line in Fig. 2 -2 9 (b ), and is equ ivalent to a potential barrier.
T h e m ost energetic electrons in the m etal can leak ou t through the barrier, result­
ing in what is called field electron emission. In Section 8.3, w e shall discuss another
barrier penetration effect, the emission o f alpha particles b y nuclei.

E X A M P L E 2.7. Analysis of wave functions and energy levels for the inversion motion
of nitrogen in the XtH 3 molecule.

S o lu tio n : T o show how much useful information we can derive from a qualitative
analysis of the wave functions, we shall now discuss the inversion motion of nitrogen in
the N H 3 molecule in more detail. Figure 2-30 reproduces the potential energy shown in
Fig. 2-28(b). Let us look at this potential energy as if it were the potential energy of a
2.8) Potential barrier penetration 85

F ig. 2-30. Potential energy for the in­

version motion in N H 3.

F ig. 2-31. W ave functions corresponding to the four lowest energy levels of the inver­
sion motion in N H 3.
86 Quantum mechanics (2.8

State la

State Oa

F ig. 2-32. Probability densities corresponding to the wave functions shown in Fig. 2-31.

simple harmonic oscillator with a bump or barrier at the center. The effect of this central
bump is a perturbation that affects the motion of the particle, mainly as it passes through
the center. As indicated before, this effect— for particles with energies such as E 1 smaller
than the height of the potential barrier— is to decrease the probability of finding the
particle in the central region. VVe can translate this into quantum-mechanical language
by saying that the bump distorts the wave functions of the harmonic oscillator potential
in the central region, decreasing their amplitude in that region. Figure 2-31 shows the
first four wave functions for the harmonic oscillator potential without the bump as dashed
lines. The actual wave functions, when the effect of the central barrier is taken into
account, are shown as solid lines. Figure 2-32 indicates the corresponding probability
densities, \ψ(χ)\2.
An analysis of these probability densities shows that |ψο[2 and \<pi\2 are almost identical.
The main difference is that |^o|2 represents a slightly greater probability of finding the
particle within the potential barrier than |^i|2. Therefore the energies E o and E i of the
corresponding stationary states must be almost equal. The same happens for |^2|2 and
I^3|2, although the similarity of these two wave functions is not as close as for ψο and ψι.
Thus the energy levels E^ and E 3 must also be very close, but not as close as E o and
E 1. However, for energies greater than the height of the central barrier (such as E ' in
Fig. 2-30), the hindering effect of the barrier is greatly reduced and the wave functions
and energy levels are essentially the same as those of the harmonic oscillator. The energy
2.8) Potential barrier penetration 87

F ig . 2-33. Energy levels for the inversion motion in N Ii,;.

levels are shown in Fig. 2-33, where the numbers correspond to the energy levels of the
N H 3 molecule. The height of the potential barrier in N H 3 is about 0.254 eV. The figure
also shows that the separation between the pair of levels Os and Oa corresponding to wave
functions ψο and or between the pair of levels Is and la corresponding to wave func­
tions i//2 and ψ:< is very small compared with the separation between the two pairs of
energy levels. Table 2-3 gives the first eight energy levels of N H 3. The symbol used to
designate each level will be explained in the next section.

T A B L E 2-3 V ib ra tio n a l Energy Levels

fo r Axial M o tio n o f N A tom
in N H s M o lecu le Relative
to the G ro u n d State

Level cm-1 * eV

3a 2861 0.3547
3s 2380 0.2950
2a 1910 0.2367
2s 1597.4 0.1980
la 986.00 0.1222
Is 950.16 0.1178
Oa 0.79 9.84 X 1 0 -'
Os 0.00 0.

*T h e unit cm-1 will be defined in Section 3.3.

I t is equivalent to I eV = 8067.5 cm-1

The most important result to be derived from this example is that when we have two
potential wells separated by a potential barrier, the lower energy levels are grouped in
closely related pairs, or doublets. I f we have three wells instead of two, we should have
triplets of closely associated energy levels, and so on. As we shall see later (in Chapters 5
and 6), this is very important in the study of molecules and solids.
88 Quantum mechanics C2.9

Fig. 2-34. Symmetrical motions: (a) pendulum, (b ) planetary orbit.

2 .9 S ym m etry. W a r v Fanviionts, anti F a r ity

Considerations o f sym m etry are often a great help to the physicist who wishes to
obtain certain kinds o f useful inform ation w ith ou t having to perform actual cal­
culations. F o r example, in the m otion o f a pendulum (o r in an y sim ple harm onic
m otion ), the position o f equilibrium 0 (F ig. 2-34a) is a center o f sym m etry. T h e re ­
fore when the pendulum is a t sym m etric positions, such as A and A ', its v e lo c ity
and acceleration must be th e same in m agnitude; the tim e required to m ove be­
tween A and 0 must be the same as th e tim e to m ove between A ' and 0 ; the
change in ve loc ity , or in kinetic energy, or in poten tial energy in goin g from A to
0 should be the same as th at from A ' to 0 , and so on. In th e case o f planetary
m otion (F ig . 2 -34b), line P Q is an axis o f sym m etry o f the o rb it and th erefore the
v e lo c ity and acceleration o f a planet a t sym m etric positions A and A ' must be
the same in m agnitude, the tim es to go from A to P and from P to A ' must be the
same, and so on. In general, if the potential energy is sym m etric relative to a certain
point, such as 0 (F ig . 2 -3 5), w e know th at when the bod y is at sym m etric positions,
such as A and A ', the dynam ical conditions m ust b e the same.
In quantum mechanics, considerations o f sym m etry are even m ore useful and
im portant than th ey are in classical mechanics. F o r exam ple, when the problem is
such th at the potential energy has a center o f sym m etry, requiring that the particle

Kpl I )
2.9) Symmetry, wave functions, and parity 89

be in the same dynam ical state at sym m etric positions, the p rob ab ility o f finding
the particle a t these sym m etric positions must be the same. Since this p robability
is given b y |^|2, w e conclude th at if A and A ' are tw o positions, sym m etric relative
to the center o f sym m etry o f the physical problem , as in Fig. 2-35, then

l * a |2 = l^ .v l2. (2.25)

T h a t is, if we plot M 2, the graph should be sym m etric rela tive to the center o f
sym m etry. N o w , assuming that the w ave functions are real, E q. (2.25) requires
that
ψΑ — ± Ψ λ '· (2.26)

Th erefore the w ave function at sym m etric points m ust be equal in m agnitude but
m ay be opposite in sign. W hen ^ a = + Ψ α ·, w e say th at the w ave function has
even parity. W hen Ψα = —Ίά ·, the w ave function has odd parity.
In general, p arity refers to the b ehavior o f the w a ve function when evaluated a t
tw o sym m etric positions. W e conclude then th at

fo r problems having a center o f symmetry, the stationary states are de­

scribed by wave functions having a well-defined parity, even or odd.

L e t us see how this im portant conclusion applies to the problem s w e have con­
sidered previously. In the potential box o f F ig. 2-G, th e point x = a/2 is a center
o f sym m etry; thus the w ave functions must be even or odd rela tiv e to x = a/2.
W e can see this clearly in Fig. 2- 8 (a ), so that we m ay say that states w ith n = I,
3, 5, . . . have even p arity while those w ith n = 2, 4, 6, . . . have odd parity. T h e
probability distributions, illustrated in F ig. 2 -8 (b ), satisfy the requirem ent stated
in Eq. (2.25), being sym m etric rela tive to x = a/2.
F o r the case o f the harmonic oscillator, the center o f sym m etry is x = 0
(F ig. 2-1 3), and the w a ve functions for n = 0, 2, 4 ,. . . have even p arity, while those
for n = I , 3, 5 ,. . . have odd p arity (F ig . 2-14). T h e p rob ab ility distribution for all
stationary states is sym m etric relative to x = 0 (F ig . 2-15).
W e used this principle o f sym m etry im p licitly when w e discussed the w a v e func­
tions for the potential well (F ig . 2-10), which has a center o f sym m etry a t x = 0.
H ow ever, the potential energy considered in E xam p le 2.6 does not exh ibit any sym ­
m etry (F ig . 2-2 0), and the corresponding w a ve functions arc neither even nor odd
(P ig- 2- 21).
T h e poten tial energy for the inversion m otion o f the N atom in the N H 3 m ole­
cule, discussed in E xam ple 2.7 (see Fig. 2-3 0), also has a center o f sym m etry, and
the corresponding w ave functions (F ig . 2-31) are even or odd. T h e even or sym ­
m etric w a ve functions are designated by s and the odd or an tisym m etric ones by a.
In T a b le 2-3, successive even and odd w ave functions are designated Os, 0a, Is, la,
etc.
A n oth er interesting fact, which we m ention in passing and which one m ay
gather b y looking at Figs. 2-8, 2—14, 2-17, and 2-31, is th at the w a ve function o f
the ground state alw ays has the same sign (in the language o f algebra, w e m ay say
90 Quantum mechanics ( 2.10

th at the w a v e function o f the ground state has no roots), w h ile the w a v e functions
fo r the first, second, third, . . . excited states cross the axis (o r change sign) once,
twice, three times, . . . (o r have one, tw o, three, . . . roots). Thus w e m ay conclude
th at
the more times the wave Junction changes sign (o r the greater the number
o f roots), the greater the energy o f the corresponding stationary state.

2. Ill Tin> T im v-Ilvp on ilfn t Svh roilinqvr Kquntion

So far w e have discussed on ly the space distribution o f the m atter field, a n d have
com puted its am plitude or w a v e function f i x ) . N o th in g has been said about the
tim e variation o f the field. T o discuss tim e dependence, w e must have an equation
containing the tim e; this equation is called Schrodinger’s lime-dependent equation.
I t plays a role in quantum mechanics sim ilar to M a x w e ll’s equations in electro­
magnetism. Schrodinger’s tim e-dependent equation is:

A2 O2V , „ . ,T .. 3 *
2m d x 2 — Ot ’ ^ ^

where w e now w rite T (x , I) instead o f ψ (χ ) for the w ave function, so that w e in­
clude both tim e and space dependence. W e see th at this equation for the m atter
field, Ί^ χ , t ), differs radically from the w a v e equation O2 Zfd t 2 = v 2 O2 ZfO x2, which
describes elastic or electrom agnetic waves, because it contains on ly the first-order
tim e d e riv a tiv e ΟΨ/ΟΙ and not the second-order tim e d erivative. In a sense
Ecp (2.27) resembles the equation fo r transport phenomena, OZfOt = a 2 O2 ZfO x2,
which is also o f first order in the tim e d e riv a tiv e and describes heat conduction and
diffusion. H ow ever, there is again an im portant difference: the im aginary factor
i = \/— I, which m ultiplies the tim e d e riv a tiv e in Schrodinger’s equation. T h e re ­
fore the field described b y E q. (2.27) is different from elastic or electrom agnetic
w aves on the one hand and diffusion or therm al w aves on the other. W e m ust re­
frain from carryin g the an alogy between quantum -m echanical fields and elastic
and electrom agnetic w aves too far.
N o te th at w e have on ly w ritten down Schrodinger’s tim e-dependent equation
and have not derived it in the same w ay that w e can establish the w a ve equation
fo r elastic w aves in a string or for electrom agnetic waves, starting from m ore basic
principles. W e could now say th at E q. (2.27) is a fundam ental law o f nature, in
the same w ay as the F aradajr-H en ry law o f electrom agnetic induction or the prin­
ciple o f conservation o f m om entum are fundam ental laws o f nature, and that its
m athem atical form is the result o f a careful analysis o f experim ental facts and in­
tu itiv e thought. T h is statem ent is essentially correct. H ow ever, w e can in fact
obtain Schrodinger’s equation if w e start from certain basic assumptions. T h is is
done in the form al th eory o f quantum mechanics, whose discussion is b ejrond this
book; however, Section 2.12 does g iv e an introdu ctory analysis. W c m ay point out
here th at the fact th at Schrodinger’s tim e-dependent equation is o f first order in
the tim e d e riv a tiv e and o f second order in the position d e riv a tiv e m ay be d irectly
2.10) The lime-dependent Schrodinger equation 91

related to the fact th at the energy o f the particle depends on the square o f the
mom entum through the relation E = p 2 / 2 m + E 1,(x ).
N e x t w e shall tr y to obtain a solution o f E q . (2.27) which is adequate to describe
stationary states. F rom our knowledge o f standing waves, w e m ay assume that
such a solution must Iiave the position and tim e variables separated. W e shall
try a solution o f the form

* { x , t) = ψ ( χ ) β - ίΕ ιι\ (2.28)

N e x t w e m ust p ro ve th at E is the energy and ψ (χ ) is the am plitude satisfyin g

Eq. (2.3). T o sec this w e note that

θΦ
_ _ = _ _
i E* W
,e - iE im . O2V
_ =
d2\p e
— iEtin

Substituting these tw o expressions in Eq. (2.27) and canceling the com m on factor
e-iE tir,' w e 0btain p;() ( 2.3) for ψ {χ ), and therefore E m ust be the total energy o f
the system. T h erefore the m atter field given b y E q. (2.28) oscillates w ith an angular
frequency
ω = E/h or E = Ιιω - hv,

in accordance w ith Eqs. (1.44) and (1.45). A s indicated before, the field expressed
b y E q. (2.28) is typical o f standing w aves because the space and tim e parts are
included in d ifferent factors. H ow ever, the im portant difference, when com pared
w ith standing w aves on strings, in air columns, or in m etallic cavities, is that the
tim e part cannot be w ritten as sin ωί o r cos oil, but on ly as e ~ 'wt = e ~ /Λ, and this
is because E q. (2.27) is o f first order in time. T h a t is, quantum -m echanical w aves
always have a com plex tim e dependence.
F o r a free particle m ovin g in the + Y -d ir e c tio n w ith m om entum p = hk, we
have ψ (χ ) = .4e‘*x. Thus the tim e-dependent w a v e function is

* ( x , 0 = i { x ) e - iE,!h = A e iikl- * 0 , (2.29)

which describes a w a ve p ropagating in the -K Y -direction w ith a phase v e lo c ity

Vp - ω/k = E / p — \v, as w e discussed in Section 1.11. T h is corroborates the
statem ent m ade in Section 2.3 th at th e w a v e function ψ (χ ) = e‘kjr corresponds to a
particle m ovin g in the -K Y-direction. S im ilarly, the tim e-dependent w a v e function
corresponding to ψ (χ ) = e ~ 'kx is '!'(x , t) = A e - ,{kz+ut), which describes a w a ve
propagating in the n egative Y -direction. H o w ever, w e cannot use cos {kx — ω ί)
or sin {kx — ω ί) instead o f E q. (2.29) to express V (x , I) for a free particle, because
these functions are not solutions o f E q . (2.27).
F o r a particle in a poten tial box,
„ a / in *xla — inr x/ a\
. / \ j · TlTTX A \B C )
V (X ) = ,1 sm — = ------------- 2Ϊ-------------
and
E t/ fi ) __ * (n x x / a - f Et/ ti)
Ψ(χ, I) = A sin e ~ iE " K = |j£. e * " " ' -
.92 Quanlum mechanics (.2.10

T h is equation corresponds to tw o w aves tra velin g in opposite directions which

result in standing waves, as in the case o f a v ib ratin g string w ith fixed ends.
A solution o f the form given b y E q. (2.28) describes a particle m ovin g w ith a
well-defined energy, corresponding to one o f the energy levels o r stationary states.
In this case,

| *(x , O l2 = [ r ( x ) e iE ll* M x ) e - iE" * ] = |*(*)|2, (2.30)

so that the p rob ab ility d ensity |Φ(χ, <)|2 is independent o f time. T h is is w h y states
described by E q . (2.28) w ere previou sly designated as stationary. W e must note,
how ever, that E q. (2.28) is not the only solution o f E q. (2.27), and th at other
solutions exist for which [Φ (χ, <)|2 is not independent o f time. T h e corresponding
states are not stationary. U sing a result from the theory o f differential equations,
w e can express the general solution o f Eq. (2.27), corresponding to nonstationary
states, as a linear com bination o f stationary-state solutions; th at is,

* ( x , I) = ^ ο ηφη(χ )β ~ ίΕ·>ιι\ (2.31.)

Tl

(T h is is sim ilar to the F ou rier analysis o f a w a v e .) T h e ab ove expression o f Φ (χ, I)

is a solut ion o f E q. (2.27), as w e m ay v e rify b y noting th at each term, being o f the
ty p e g ive n in E q. (2.28), is a solution o f E q. (2.27), and th at th eir sum is also a
solution, since E q. (2.27) is a linear homogeneous differential equation.
A s a m ore concrete illustration, let us consider the case in which Ψ(χ, I) can be
expressed as the sum o f tw o stationary term s; th at is,

* (x , 0 = cpkie- ^ · ' " 1 + c 2 t 2 e - iEi ," >. (2.32)

T o obtain the initial w a v e function, w e set 1 = 0, resulting in

Ψ(Χ, 0) = C l^l + C2^ 2·

W e can com pute the coefficients C1 and c 2 b y a straightforw ard m athem atical
m ethod if w e know Φ (χ, 0) (see Problem 2.37). H ence w e can determ ine Sk(x, t) if
we know the initial w ave function Ψ(χ, 0 ).
T h e p ro b ab ility distribution corresponding to Ί^ χ , i) is

P (x ,t) = | Ή χ ,ί)|2

= { c U * c <E,,IA + cU * 2 eiE*,lh} { c 1* Ie - <£,‘ + c 2 i 2 e ~ iE^ H}

= M ,|2 + |c2vk2|2 + c t c i M U - * * ' - * ' " * +

+ ο ϊο 2 φ *φ 2 β<(Ε' - Ε*)," ί. (2.33)

T hus P (x , t) is not constant, but contains term s th at oscillate w ith the angular
frequency ω = (E 1 — E 2)/h or th e linear frequency v = ( E i — E 2 )/h. T h erefo re
 The lime-dependenl Schrodinner equation 93

the state described b y the given t) is not stationary. T h is result gives us a

clearer idea o f the difference between stationary and nonstationary states. A lth ou gh
for stationary states |Ψ(χ, i)|2 is independent o f time, in nonstationary states
|Ψ(£, <)|2 contains a series o f oscillatory terms w ith frequencies v = ( E n — Ε η·)/Ιι.
T h e w a v e function given b y E q. (2.32) m ay describe a system during a transition
between stationary states E i and E 2- I f th e particle suffering the transition is
charged, w e m ay say that during the transition the p article behaves as an oscillator
having a frequency given b y B oh r’s equation (1.29), v = ( E i — E 2 )/h, and there­
fore is capable o f em ittin g or absorbing electrom agnetic radiation o f the same
frequency. H ence the form alism o f quantum mechanics in c o rp o ra te B oh r’ s equa­
tion E I — E 2 = hv in a natural way.

E X A M P T E 2.8. Discussion of the wave function describing the inversion of the N H 3

molecule.

F ig. 2- 36. Description of the inversion t = wft/ Δ Ε

motion in N H 3 by means of time-dependent
wave functions.

S o lu tio n : Suppose that the N atom is initially (most probably) in the right potential
well ground state (see Fig. 2-30). Therefore the initial wave function must be large at
the right well and very small at the left well. The initial wave function then may be
expressed as

* ( * , 0) =

and it has been represented in Fig. 2-36(a). Recalling the shape of the functions ψο and
ψ ι in Fig. 2-31, we may also write, as a good approximation,

Ί^ χ , 0) = Ψ/ί = φο + i i -

The wave function after a certain time I is given by

T'tx, I) = -f- tjsI1**,

Setting A E = E i — Eo, we can write this expression as

Ψ(χ, <) = (ψο + ψΐβ ίΔε,Μ)β * ο ·'\

M Quantum mechanics {2.11

A t a time t = ττΙι/ΔΕ, the exponent in the parentheses is — I, and we have

Ψ (χ ,Ι) = (φο — Φ i)e -li;o,/ft =

where, from the shapes of φο and φ j as shown in Fig. 2-31, we see that Φ/, ** φο — φ \
is concentrated on the left. This is also shown in Fig. 2-36. Therefore the particle— the
N atom in our example— is (most probably) in the left potential well. In other words,
the N H 3 molecule has been inverted. Obviously at a time I = 2πΙι/AE, the particle is
again back on the right. Therefore the frequency of inversion of the molecule is given by
v = ΑΕ/2τ1ι = (E 1 — Eo)/h. The experimental value for v is 2.38 X IO 1 0 Hz, from
which we can calculate the energy difference Ei — Fo as 9.84 X 10_o eV. This is the
value given in Table 2-3.

2.11 Trnnsitioii V ro b a b iH tirs anil S rlrrtion Mtulrs

I t is logical that at this m om ent the student should ask the follow in g question:
H ow can quantum mechanics predict when a transition is going to occur? In other
words, if an atom , molecule, or nucleus is in an excited state, how m ay w e know
when and where it is going to jum p to a state o f low er energy? O r if the atom ,
molecule, o r nucleus is subject to an external electrom agnetic field, how m ay we
determ ine w hether it absorbs energy and passes to an excited state? T h e answer
to these questions is th at we cannot tell the exact tim e at which the transition will
take place, but th at for each jum p, let us say from state i to state /, there is a
lransilion probability per unit tim e, Ti/, which w e can com pute according to the
laws o f quantum mechanics and the interactions responsible for the transition. T h e
larger Ti/, the m ore lik ely it is th a t the transition w ill occur. O f course, if T 1; - 0,
the transition is impossible or forbidden. T h is result implies that not all transitions
which satisfy B o h r’s equation, v = (/s' — /s’) //1, arc possible, because, in addition
to the conservation o f energy, other considerations enter into the process. An gular
m om entum , for exam ple, must be conserved. Also, because o f the space sym m etry
o f the system (th a t is, the p arity o f the w a ve functions), it m ay not be possible for
the w a v e function o f th e initial state to undergo an adjustm ent so th at it w ill be
transform ed into the w a v e function o f th e final state b y a proper rad iative process.
T h is lim itation in the possible transitions g ives rise to selection rules. These rules
state which are the m ore probable or allowed transitions; i.e., fo r which the transi­
tion probabilities have large values.
D uring an electrom agnetic transition, th e system m ay behave as an oscillating
electric o r m agnetic m ultipole, and therefore xve have electric or m agnetic dipole,
quadrupole, etc., transitions, each characterized b y its ow n transition prob ab ility
and selection rules. U sually the m ost probable transition is the electric dipole, fol­
low ed b y the m agnetic d ipole and the electric quadrupole. H ighcr-order m ultipole
transitions h ave v e ry small transition probabilities and are, in general, disregarded
except for some special cases in nuclei. T ransition s for which the electric-dipole
transition p rob ab ility is n ot zero are called first-order allowed. W h en the electric-
dipole-transition p rob ab ility is zero, the transition is called first-order forbidden,
even though such a transition m igh t still occur at a much low er rate, as a mag­
netic dip ole or an electric quadrupole transition (o r even a highcr-order m ultipole
transition). F o r exam ple, the electric-dipole transition p rob ab ility o f a harm onic
2.11) Transition probabilities and selection rules 95

oscillator is d ifferent from zero on ly if

An = ±1 (2.34)

wh'ere Δ?ι = « / — »,·, which gives the selection rule for the first-order allowed
transitions o f the oscillator. T h is means that the first-order allowed transitions o f
a harm onic oscillator are from one neighboring state to another; i.e., from a state
whose quantum number n differs from its neighbor’s b y ± 1 . Thus th e energy
absorbed (A n = - fl) or em itted (A n = — I) in one transition, according to
E q. (2.21), is

IE f - Ej\ = hw = hv, (2.35)

where v is the frequency o f the harm onic oscillator. C om parin g Eqs. (2.35) w ith
B oh r’s equation, w e see th at the harmonic oscillator can em it or absorb radiation
o f on ly one frequency, which is equal to its own (th e classical oscillatory frequ ency)
and so its spectrum is lim ited to on ly one frequency.
W hen a system is in an excited state it w ill remain in the excited state for on ly
a certain length o f tim e because o f the p rob ab ility o f its ju m p in g into a low er
energy level. T h e average lifetim e o f an excited state is inversely proportional to
the total transition p ro b ab ility o f that state; i.e., the sum o f the probabilities o f
the transitions to all the low er energy levels into which it. m ay jum p. T h e lifetim e
o f the ground state o f an isolated system isob viou sly infinite, since the system
cannot ju m p into a low er level. L ife tim e s for allow ed atom ic and m olecular tran­
sitions are o f the order o f IO- 8 s, while the lifetim es for nuclear transitions range
from IO- 8 to IO -14 s.
A lth ou gh transitions in which a system in an excited state em its energy b y
jum ping to a state o f low er energy m a y occur spontaneously, it is necessary, if a
system is to absorb energy, for an external action to intervene. I f the system is
in itially in an excited state, this external act ion m ay also induce emission o f energy,
in ad dition to the spontaneous energy emission as a result o f the perturbation
produced in the system . T h is is called stimulated emission, and is v e ry im portant
in m any cases. T h e three processes— absorption, spontaneous emission, and stim u­
lated emission— are illustrated in Fig. 2-37. In E xam ple 13.5, w e shall obtain the
relation between the spontaneous and stim ulated transition probabilities.

In ith il FinnI In itial Final In itia l Final

state state
E2

(a ) A bsorption (I») Spontaneous (c ) S tim u lated

emission em ission

Fig. 2-37. Radiative processes: (a) absorption; an incident photon is absorbed; (b)
spontaneous emission, resulting in a photon; (c ) stimulated emission under the action
of an incident photon.
96 Quantum mechanics

2.12 T h e F o r m a l T h eo ry o f lfnantnm blvvhanivn

T liu s far w e have developed a quantum theory for atom ic system s based on
Schrodinger’s equation. W ith the aid o f the w a v e functions resulting from the
solution o f Schrodinger’s equation, w e can obtain inform ation about the possible
energy levels o f the system, the p ro b ab ility o f finding the system a t a particular
region o f space, the p ro b ab ility o f a transition from one energy level to another,
the frequency o f the electrom agnetic radiation em itted or absorbed, and so on.
H ow ever, so far it would seem th at the on ly inform ation w e can extract from the
laws o f quantum mechanics concerns the energy o f the system. T h is is not so.
I t is possible to express the principles o f quantum mechanics in a form al way,
which makes it possible for us to obtain all the necessary inform ation about a
physical system. W e shall now present, in a sim plified way, this formal theory.
C onsider first the one-dimensional problem . Schrodinger’s equation (2.3) can
be w ritten in the form

(2.36)

W hen w e w ro te the left-hand side, w e factored out the w a ve function ^ ( i ) as if it

w ere a common factor o f the quantities inside the bracket. H ow ever, each term
in the bracket must act on, or operate on, ψ (χ ) according to its own nature. T h a t
is, E p(x ) m ultiplies φ (χ ) but <l2 /dx 2 produces the second d e riv a tiv e o f ψ (χ ). In
m athem atical language w e m ay say that the expression

(2.37)

appearing inside the brackets is an operator*, which, when it acts on a function

ψ (χ ) (th a t is, Η ψ (χ )), produces a new function as a result o f a series o f m athe­
m atical operations exp licitly contained in the definition o f H. In particular
E q. (2.36) can be w ritten in the sym bolic form,

Hφ (χ ) = Ε φ (χ ), (2.38)

which means th at the effect o f H on φ {χ ) is to m u ltip ly φ (χ ) b y the constant E .

O bviou sly when H operates on an arb itra ry function the result is not necessarily
the same function m ultiplied b y a constant, but in general it is another, different
function. T h ose functions satisfyin g Etp (2.38) are called the proper functions o f
the operator H, and the corresponding values o f E are the proper values o f the
operator.
F o r an arb itra ry operator A, the proper functions and the proper values are
those satisfying the equation

Α φ {χ) = α φ (χ). (2.39)

* Operators will be designated by sans-serif symbols.

2.12) The formal theory of quantum mechanics 97

T h ere arc, in general, a scries o f proper values Ct1, a2, a3l . . . and a series o f associ­
ated proper functions ψ|. ψ2, Ψ3, . . . , which depend on the nature o f the operator
and on the m athem atical boundary conditions. These proper functions are a con­
sequence o f the physical properties o f the system . In some cases there are several
w ave functions corresponding to a given proper value; in that case, the proper value
is said to be degenerate.
In quantum mechanics the operators belong to a class called Itennitian (nam ed
a fter the French m athem atician C. H erm ite). These operators satisfy the condition

(2.40)

for all functions Φι and Φ2 which satisfy the required boundary conditions. It can
be shown that

the proper values o f Iierm itian operators are real and that their proper
fun ction s are orthogonal.
T h at is,
(2.41)
All space

where ψ, and ι/q are proper funct ions belonging to proper values a, and a j o f A.
T h e operator H given b y E q. (2.37) plays a v e ry im portant role in quantum
mechanics and is called the ham iltonian operator o f the system. In classical meehan-
ics the total energy is called the ham iltonian when it is expressed in terms o f the
momentum and the coordinates o f the system . Thus fo r a part icle m ovin g in one
direction the classical hamiltonian is

(2.42)
Tfclassical — 2?7l ^

W e m ay correlate the classical and quantum -m echanical hamiltonians in a v e ry

sim ple w ay. B y com paring Eqs. (2.37) and (2.42), w e see th at w e m ay transform
the classical ham iltonian into the quantum -m echanical ham iltonian operator by
m aking the correspondence

(2.43)

[T h e minus sign in E q. (2.43) is on ly a m atter o f convenience.! F or m otion in three

dimensions, the classical hamiltonian is

(2.44)

where r is the position vector o f the particle and p 2 = p I + v l + P t· T h o logical

extension o f the correspondence expressed b y E q. (2.43) is

(2.45)
98 Quantum mechanics ( 2.12

U sing the ve cto r operator V, read del, defined by

d I d . a
V = u x - — r U u -— |- Hj — I
ckr dy ‘ dz

w e m ay w rite E q. (2.45) in the m ore com pact form,

p -* — ihV. (2.46)

R ep la cin g p in the classical ham iltonian b y the operator — ihV, we g et the quan­
tum-mechanical operator

h - - ^ ' ! + £' w

ft2 / a2 . a2 . a2\ , n ,.
2 m \d x 2 ' d y 2 + d z 2) + p (r)' ^2 ' 4 7 )

O perating w ith H on a function ^ (r ), w e have

I f φ is a proper function o f H, w e have H f = Εψ, where E is th e proper valu e of

H, or

h2 ZaV a V , a2A
“ 2 m ^ + W + W )+ p( ¥ = *'

T h is is just Schrodinger’s equation in three dimensions, as stated in E q. (2.9), and

therefore we m ay say that E q. (2.47) gives the quantum -m echanical ham iltonian
operator o f a particle in three dimensions.
On the basis o f relation (2.46), w e m ay state the first p rin cip le o f quantum
mechanics, as follows:

I . T o every physical quantity .4 (r, p ) , which is a fu n ctio n o f the posi­

tion and momentum o f a particle, there corresponds a quantum operator,
obtained by replacing p by — ih V ; that is, A (r, — fftV).

T h erefo re the ham iltonian operators (2.37) or (2.47) are the quantum operators
corresponding to the total energy o f the system fo r m otion in one and three dim en­
sions, respectively. Sim ilarly, to the kinetic energy E k = p 2 /2m, there corresponds
the operator — {h 2 / 2 m )V 2 in three dimensions, or — (h 2 /2 m )d 2 /dx 2 in one dim en­
sion. T a b le 2 -4 summarizes the quantum operators for several physical quantities.
T h e second p rin cip le o f quantum mechanics states:

I I . The only possible values that can be obtained when a physical quan­
tity A (r , p ) is measured are the proper values o f the quantum operator
A (r, — ih V ).
2.12) The formal theory of quantum mechanics 99

T A B LE 2 -1 Q u a n tu m O perators

Quantity Classical definition Quantum operator

Position r r
Momentum P —ifiV
Angular momentum r X p — ih r X V
Kinetic energy p 2 /2 m — (A2/2ro)V2
Total energy p 2 / 2 m + E pI r) — (ft2/2m)V2 + Eptr)

In this w a y we m ay determ ine the values not on ly o f the energy but o f an y other
physical qu an tity. T h is principle, therefore, tells us what physical inform ation
w e m ay extract concerning a system . Stating the principle in m athem at ical terms,
w e m ay set up the operator equation

A (r , — ί’Λ ν)ψ = af/. (2.48)

N ex t we shall find the possible values o f a and the functions ψ th at satisfy this
differential equation w ith the required boundary conditions. T h e proper values
Oj, Ct2, a 3, . . . are the on ly possible results o f a measurement o f .4. W e also say th at
the proper functions f \ , ψ2, Ψά·. ■ ■ ■describe the possible states o f the system insofar
as the physical qu a n tity A is concerned.
O bviously i f the system is in a state described b y the proper function ψ„ cor­
responding to the operator A , then the value o f the physical qu a n tity .4 is a „ .
B u t w h at happens if the system is in a state described by a function Φ which is
none o f the ψ„ solutions o f E q. (2.48)? In such a case, we say that .4 does not have
a precise value. E xpan din g the w a ve function Φ in terms o f the proper functions
ψη o f the operator A, we obtain

Φ = Cpffl + Cnff2 + C-A3 H / ο ηψη.

W hen the functions are orthogonal, then obviou sly

cn = J ψ*Φ (Ir. (2.49)

T h erefore th e third p rin cip le o f quantum mechanics states that

III. When the state o f the system corresponds to the wave fun ctio n Φ ( γ ) ,
the probability o f obtaining the value an as a result o f a measurement o f
the physical quantity .4 (r, p ) is |c„|2, where c„ is given by Eq. (2.49)
and φ„ is the proper fu n ction o f the operator A (r, — t'AV) corresponding
to the proper value a„.

I t can be shown th at E q. ( 2. 1) is sim ply a special application o f this principle when

the physical qu a n tity measured is just the position o f the particle.
100 Quantum mechanics (2.12

A ccord in g to the third principle, when the w ave function Φ is not a proper func­
tion o f A, w e cannot say what the exact value o f A is, and if w e repeatedly measure
.4, w e obtain m any different results, each with a certain probability. W e m ay,
how ever, speak o f the average o r expectation value o f A in the state described b y Φ.
A s a corollary o f the third principle, w e can show that.

the average or expectation value o f a physical quantity A ( r , p ) when the

state o f the system corresponds to the fun ction Φ (γ) is

Φ A (r , — ί!ιΧ )Φ d r. (2.50)
- I , AU space

T o handle E q. (2.50), we must first operate w ith A on Φ, then m ultip ly by Φ*,

and finally integrate. E quation (2.50) is correct if the function Φ is norm alized to
one; th at is, if / φ * Φ γ/τ = I. B u t if Φ is not norm alized to one, w e must w rite
instead
/φ*ΑΦ d r .
Βνβ_ /Φ*Φ dr ' (20l)

T h e principles we have stated are static in the sense that th ey g iv e no inform a­

tion about the tim e evolu tion o f a system. T o obtain a dynam ic theory, w e need
the fou rth p rin cip le o f quantum mechanics:

IV . The time evolution o f a physical system is described by the equation

ih ™ = ΗΦ, (2.52)

where H is the ham iltonian operator o f the system.

W e sec th at E q. (2.52) is identical to E q. (2.27) in one dimension when H is

given b y E q . (2.37). A p p lyin g the idea o f operators, w e m ay say that w e can ob ­
tain the dynam ical equation (2.52) b y replacing the energy E in E q. (2.38) b y the
operator ih d / d t.' T h a t is,

* - . « £ · (2.53)

W e shall not elaborate further on the form al th eo ry o f quantum mechanics; the

principles w e have stated are sufficient for the purpose o f this book.

E X A M P L E 2.9. Find the average value of the momentum of a particle in a potential

box, given that the wave function corresponds to one of the stationary states.

S o lu tio n : W e obtained the wave functions of a particle in a one-dimensional box in

Section 2.5 as
2.12) The formal theory of quantum mechanics IOI

Since the functions are normalized, we use Eq. (2.50). Therefore

P ave

since the operator corresponding to p is —ihd/dx. But HfznZdx — \/2/a(nir/a) cos nirx/a.
Therefore

. . 2nir [ . η τχ W i ,
Povo = —i ft —— / s m cos dx = 0.
a2 J -a o a

This may seem to contradict Eq. (2.13), which states that the momentum of a particle
in a box is p = nirh/a. However, the value p = ητΐι/α gives the magnitude of the momen­
tum. But momentum is a vector quantity and a particle in a box moves back and forth
in a symmetric way, changing the direction of its momentum. Thus it is natural that
pave ~ 0.

E X A M P L E 2.10. Matrices associated with a physical quantity.

S o lu tio n : Let us consider the proper functions fzi , fz2 , f h . . . of the hamiltonian; i.e.,
those satisfying the equation Hfzn = Efzn- Given that .I is another physical quantity,
we may obtain the series of quantities

-Imn = Jfzm tyndr (2.54)

for each pair of functions and fz„. These quantities can be arranged in the matrix form:

In Λ 12 Λ 13 ·.. Au

I 21 Λ 22 .123 ··. -12»

131 Λ 32 .1 33 ··. .4 3»

I mI Am 2 Λ m3 . . . aL

This array is called the matrix of .4; the .1„„ are the matrix elements. The elements
- I n , .422, · · · -Inn, · ■ ■ are called the diagonal matrix elements because of their location
in the matrix. T o compute the matrix of an operator, one does not necessarily have to
use the proper functions of the hamiltonian; the proper functions of any other operator
may be used instead.
The calculation of matrix elements is very important in several quantum problems.
We shall illustrate only one example. The matrix elements of the position vector arc

wn = Jfzmrfzn dr.

I t can be proved that the transition probability from state t into state/ with the emission
or absorption of electric dipole radiation of energy Ziw = E, — Ef is given by

aV - S S S ? I-"·1· ( 2 -5 5 )
102 Quantum mechanics

Thus if r,/ = 0, the transition is first-order forbidden. In this way we obtain the selection
rules mentioned in Section 2.11. The state of polarization of the radiation is determined
by the components of r,/. For example, if χ,·/ = j/,/ = 0 but z,/ ^ 0, the the radiation
emitted or absorbed is polarized parallel to the /-axis. Since the energy emitted in the
transition is fto>, we have that the rate of energy radiation is

d li r, r ε ~ω > I I2
i t = h u T it = w

A fter comparing this with the result of Example 1.1 for a classical oscillator, we conclude
that during the transition the electron behaves as an electrical dipole of angular frequency
ω and an amplitude 2[r,/|.

R p fo rv m -O H

1. “ Quantum-Mechanical Tunneling," J. Former, Am. J . Phys. 34, 1168 (1966)

2. “ The Philosophical Hasis of Bohr’s Interpretation of Quantum Mechanics,” K. IIall,
Am. J. Phys. 33, 624 (1965)
3. “ Quantum Mechanics as a M odel,” T . Bucht Am. J . Phys. 34, 653 (1966)
4. “ Interpretation of Quantum Mechanics and the Future of Physics,” E. Witmer, .lm.
J. Phys. 35, 40 (1967)
5. Elements of ll'ave Mechanics, N. M ott. Cambridge: Cambridge University Press,
1962, Chapters I, 2, 3, and 4
6. Introduction to Modern Physics, F. Richtmyer, E. Kennard, and T. Lauritsen. New
Y ork: McGraw-Hill, 1955, Chapter 6, Sections 96-102
7. Elementary Wave Mechanics, W. Heitler, second edition. Oxford: Oxford University
Press, 1956, Chapters I and 2
8. Atomic Spectra and Atomic Structure, G. Herzberg. New Y ork: Dover Press, 1944,
Chapter I
9. Structure of Matter, W. Finkelnburg. N ew Y ork : Academic Press, 1964, Cha))ter 4
10. Quantum Theory of Matter, J. Slater. N ew Y ork: McGraw-Hill, 1951, Chapters 1,2,
and 3 '

P r o M o n tH

2.1 A particle is represented by the wave
function ψ (χ) = sin kx. Plot
the wave function φ (χ ) and the probability
distribution |^(.r)|2. Estimate the uncer­
tainty in the position and in the momentum
of the particle.
2.2 Show that R-J-T = I for a stream of
particles impinging on a potential step of
height Eo when E > Eo (refer to Ex­
ample 2.2).
2.3 W hat is the effect on the energy levels
of a one-dimensional potential box as the
size of the box (a) decreases? (b) increases?
2.4 Consider an electron in a one-dimen­
sional potential box of width 2.0 A. Cal­
culate the zero-point energy. Using the
uncertainty principle, discuss the effect of
incident radiation designed to locate the
electron with a 1% accuracy (that is,
Ax = 0.2 A).

2.5 Estimate the zero-point energy of an
electron confined inside a region of size
IO-14 m, which is the order of magnitude of
nuclear dimensions. Compare this energy
with both the gravitational potential energy
and the coulomb potential energy of an
electron and a proton separated the same
distance. On the basis of this comparison,
discuss the possibility that an electron
can exist within a nucleus.
2.6 Calculate the zero-point energy of a
neutron which is confined within a nucleus
which has a size IO-15 m.
2.7 Show that the fractional energy dif­
ference A E / E between any two adjacent
levels of a particle in a box is given by
( 2n + I )/n2.
2.8 Normalize the wave functions for a
particle in a potential box, given by
Eq. (2.18), showing that C = V 8 /abc =
V 8/F, where V is the volume of the box.
2.9 Prove that the three-dimensional wave
functions given in Eq. (2.18) are orthogonal.
2.10 Plot the function g(p) given in Ex­
ample 2.4 versus p, and compare with
Fig. 2-12. Explain the difference.
2.11 Show that the volume of phase space
corresponding to a particle moving within
a region of volume V and having a momen­
tum between p and p + dp is 4π \'ρ 2 dp.
Recalling that the minimum size of a cell
in phase space within which a particle can
be localized is h3, find the number of quan­
tum states with momentum between p and
p + dp accessible to the particle. Compare
with the results given in Examjjle 2.4.
2.12 Show that the energy levels and wave
functions of a particle moving in the X T -
plane within a two-dimensional potential
box of sides a and b are
E = (π 2 h2 /2 m) (n 2 /a 2 -)- n\/b2)
and
Φ = C sin (ηιττχ/α) sin (nziry/b).
Discuss the degeneracy of levels when
a = 6. Find the normalization constant C.
2.13 Referring to Problem 2.12, if the
two-dimensional box is very large, but has
Problems 103
equal sides, find the number of quantum
states (a) with energy between E and
E T dE, (b) with momentum between p
and p -f- dp.
2.14 Verify by direct integration that
wave functions φο and \f/\ for the harmonic
oscillator (Table 2-2) are normalized.
Also verify that ψι> is orthogonal to ψ\
and ψ2.
2.15 Calculate the zero-point energy and
the spacing for the energy levels (a) in a
1-dimensional harmonic oscillator, with an
oscillatory frequency of 400 Hz, (b) in a
three-dimensional harmonic oscillator with
an oscillatory frequency of 400 H z1 (c) in
the CO molecule, if the two atoms oscillate
with a frequency of 6.43 X IO11 Hz.
2.16 The general expression of the solu­
tions of Schrodinger’s equation for the
harmonic oscillator is
= N nH n(OX)e- * * '2' 2,
where N n = \Ζα/πΐ'2 2"ηΙ is the normali­
zation constant, a = s/moi/fi, and the
functions H n(ax) are called Hermite poly­
nomials, defined by
/ / „ (* ) = ( — l ) " e {2 ( e -£2) .
Write the first four wave functions (n — 0,
I, 2, 3) and compare with the expressions
given in Table 2-2.
2.17 The wave functions for a three-
dimensional harmonic oscillator can be
written as
ψη, η2 η$(%, V, Z) ~ N niN niA n^
X H ni(OX)H ni(a y )H n3 (Ca)eS S ^ ,
where the different quantities are as de­
fined in Problem 2.16. The energy of
the oscillator is E = (η + §)Λω, where
n = m + «2 + « 3. Show that the degen­
eracy of each state is g = £ (n -f- l )(n -f- 2).
Fully write out the wave functions corre­
sponding to n = 0, I, and 2. Note that
the wave function for w = 0 is spherically
symmetric. .Vnalyze the shape of the wave
functions for n = I.
IOb Quantum mechanics

Ep

F ig u re 2-39

Kp

F ig u re 2—10 F ig u re 2—11

Kp

F ig u re 2—12

2.18 W ia t is the effect on the energy
levels of a one-dimensional potential well
as the depth of the well (a) decreases?
(b) increases? Repeat the analysis, con­
sidering that the width changes but the
depth remains constant.
2.19 Discuss the effect on the energy
levels and wave functions of a potential
well of range a when a hard core of range b
is added, as shown in Fig. 2-38. [H int:
See Examples 2.5 and 2.6.)
2.20 Given a potential well of depth
E o and width a (Example 2.6) draw the
possible wave functions for the bound
states if v
(a) E oa 2 < Tr2E2/Sm,
(b) TT2 fi2/Sm < E oa 2 < 9ir2A2/8m,
(c) Ihr2 Ii2 /Sm < E oa 2 < 25rr2h2/Sm.
2.21 Estimate the well depth E o for a
neutron in a one-dimensional rectangular
well of width 3 X IO-15 m, given that its
binding energy Ei, is 2.0 MeV, and assum­
ing that only one energy level is possible.
2.22 Equation (2.23), Zr, cot £,a = —a,
may be solved graphically in the following
way: Define £ = k,a, η — a a, and
P = (V 2 m E o / h )a . Therefore £2 + η2 =
P2. Also from Eq. (2.23), η = — ξ cot ξ.
With £ as abscissa and η as ordinate, plot
η = — £ cot £ and show that the circle
£2 jT V2 = p 2 intersects the curve once,
twice, three times, etc., depending on the
value of p. The points of intersection cor­
respond to the allowed values of E o a 2.
Show that these values are consistent with
the values of E oa 2 given in the text.
2.23 For the square potential barrier of
Fig. 2-23, determine the coefficients B, C,
D, and .1' in terms of the coefficient A for
(a) E < E o and (b) E > Eo-
2.24 Write the wave functions in each of
the regions of the potential energy shown
in Fig. 2-39. Also sketch the wave func­
tions. Consider that the incident particles
come from the left and discuss the three
distinct cases in which E < Eo, E o < E <
E'o, and E > E'0.
Problems 105
2.25 Repeat the preceding problem for a
case in which the particles are initially in­
cident from the right.
2.26 Consider the potential energy shown
in Fig. 2-40. Discuss the general mathe­
matical expression and the shape of the
wave function for a particle incident from
the right when its energy is (a) E < Eo,
(b) E 0 < E < E'o, and (c) E > E'o. R e­
peat the last two cases for a particle which
is incident from the left.
2.27 Write the wave function in each of
the regions of the potential energy shown
in Fig. 2-41. Also sketch the wave func­
tions. Consider a particle incident from the
left, first with E < Eo, and then with
E > Eo- Is there a possible stationary
state for a particle initially in region (3)?
2.28 Write the wave function in each of
the regions of the potential energy shown
in Fig. 2-42. Also sketch the wave func­
tion.
2.29 A particle moves rectilinearly under
the action of a uniform electric field S so
that its potential energy is E p = — Sx.
(a) W'rite the Schrodinger equation for this
motion, (b) Make a sketch of the wave
functions for an energy E larger and smaller
than zero. Is the energy quantized?
2.30 Given the potential energy shown in
Fig. 2-43, sketch the wave functions for a
particle coming from the right and having
a total energy that is (a) negative, (b) be­
tween zero and Eo, (c) larger than Eo.
H ow does the wavelength of the particle
change as the particle moves in the regions
x > 0 and x < 0, if the total energy is
larger than E o l Repeat for a case in which
the particle comes from the left. This
situation corresponds to the potential
energy of an electron in a metal when an
external electric field G is applied.
2.31 A particle moves under the potential
energy E p(x ) = — Foe- " ' 2, (a) Plot E p(x ).
(b) Make a sketch of the wave functions
when the total energy is both negative and
positive, (c) Do you expect to have quan­
tized energy levels for certain ranges of the
energy? (d) Estimate the zero-point energy
i06 Quantum mechanics
'j I'
of the particle. (H in t: N ote that for ener­
gies close to — Eo the particle oscillates
with a frequency ω = [(d 2 E p/dx2 )/ m ]U2.)
2.32 Show that for the Hermite poly­
nomials defined in Problem 2.16,
/ / .(- ί) =
if n is even and
ΙΙΛ -ΰ = -U n it)
if n is odd. Conclude from this that the
wave functions for the one-dimensional
harmonic oscillator have even or odd
parity depending on whether n is even or
odd. Also show that the parity of the
three-dimensional harmonic oscillator of
Problem 2.17 is even (odd) depending on
whether n is even (odd).
2.33 Show that the wave functions of a
particle in a potential box of Eq. (2.18)
have even (odd) parity if n = ni + «2 + «3
is odd (even).
2.34 Given the potential energy shown in
Fig. 2-44, write the wave function for each
region and sketch the wave functions and
energy levels for E < Eo and E > Eo-
N ote that the wave functions are symmet­
ric (even) and antisymmetric (odd). Dis­
cuss the effect on adjacent energy levels as
either Eo or b becomes very large.
2.35 A particle moves with the potential
energy shown in Fig. 2-45. Plot the wave
E„
F ig u re 2-45
functions and the probability distributions
for the three lowest energy levels. Recog­
nize that the three levels have very close
energies. Make a general sketch of the
energy levels.
2.36 Consider the time-dependent wave
function for a beam of free particles as
given by Eq. (2.29), where \A\2 is the
average number of particles per unit
volume. Show that the number of particles
crossing a unit area per second (i.e., the
particle flux) is h\A\2 k/m.
2.37 Given that
Φ (*, i) = + C2’/'2(z )c _ ‘a'2'/a,
where the proper functions φι (x ) and φ/ζ(χ)
are orthogonal and normalized, show that
Ci = J ^ t(Z )1POr, 0) dx
and ·
Co = j φ * (χ )* (χ , 0) dx.
This shows that the wave function at any
time can be found in terms of the initial
wave function Ψ{χ, 0). Extend the result
to the case in which
ΊΌ τ, t) = ^ c„\l/n(x )e ~ 'En‘" ‘·
n
2.38 Show that the frce-particle wave
functions φ (χ ) = e±,k* are proper func­
tions of the momentum operator corre-

spending to the proper values ±hk,
respectively.
2.39 Indicate which of the following func­
tions are proper functions of the operator
d/dx: (a) Cirt, (b) eat, (c) sin kx. Indicate
in each case the proper value. Repeat for
the operator d~/dx2.
2.40 Show that the momentum operator
— ifid/dx is hermitian. [H in t: Integrate
the expression on the left of Eq. (2.40) by
parts, with A replaced by the momentum
operator, and take into account the be­
havior of wave functions at d b » .]
2.41 Find the average or expectation
values of x, x2, p, and p 2 for the n = 0 and
n = I states of the linear harmonic
oscillator.
2.42 Find the average or expectation
values of x, x 2, p, and p 2 for the ground
and first excited states of a particle in a
one-dimensional potential box.
2.43 Write out fully the operators corre­
sponding to the three rectangular com­
ponents of the orbital angular momentum
L = r X p.
2.44 The commutator of two operators A
and B is A B — BA and is designated by the
symbol [A , B], Show that
[x, ρχ\ψ = ilop,
[y, PxWr = o,
and
[z, p M = 0,
where \p is an arbitrary function. Usually
the wave function is not explicitly written
and the relations are written as [x, px] = Hi,
[l/, Pil = 0, and [z, px] = 0. (Commuta­
tors play a very important role in quantum
mechanics.)
2.45 Find the matrix elements 201, * 02,
pot, and po2 for the coordinates and
Problems 107
momenta of a linear (one-dimensional)
harmonic oscillator.
2.46 A particle moves in a one-dimen­
sional potential box of width a. From the
normalized wave functions find the matrix
elements x„m and p nm. Show also that
Pnm = im (XnmI nm, where
ω„„, = (E n — E m)/h.
2.47 Find the selection rule for the elec­
tric dipole transition of a particle in a one­
dimensional potential box. [H in t: Recall
Example 2.10.)
2.48 Show that if <pi and <p> are indepen­
dent proper functions of a linear operator
corresponding to the same degenerate
proper value, the function φ = c\\p\ -f- ο-ζψ-ζ
is also a proper function of the operator
corresponding to the same degenerate
proper value. Show also that if <p\ and \p>
are not orthogonal it is possible, by a choice
of constants, to make the proper function
φ normalized and orthogonal to \pi. This
result is important because it shows that
the proper functions corresponding to
degenerate proper values can always be
assumed to be orthogonal. Extend the
method to the case of three proper func­
tions <pi, ψ>, ψ:\, by making two linear
combinations φ ι and φ·> of these three
functions that are normalized and orthog­
onal to ψι.
2.49 The curvature of a function ψ (χ) is
proportional to d2 \p/dx2. Using Schrodin­
ger’s equation, show that if E < E p(x ),
the wave function \p(x) is concave toward
the χΥ-axis, and that if E > E p(x ), the
wave function \p(x) is convex toward the
.Y-axis. Check this result with the plots
of wave functions considered in this
chapter.
 3
ATOMS WITH ONE
ELECTRON

3.1 Introduction
3.2 The Hydrogen Atom
3.3 The Spectru
3A Quantization o f A ngular M om entum
3.5 One-Electron Wave Functions Under Central Forces
3.6 The Zeeman Effect
3.7 Electron S p in
3.8 A d d ition o f A ngular Mom enta
3.9 S p in -O rb il Interaction
3.2) The hydrogen atom 109

3.1 In trod u ction

W e shall begin our study o f atom s b y sum m arizing our fundam ental ideas about
atom ic structure. E v e r y atom has an overall dimension o f abou t IO- 9 m. I t is
composed o f a rela tively m assive nucleus (whose dimensions are o f the order o f
IO -14 m ) about which m ove a number o f electrons, each o f charge — e, occupying the
rest o f the atom ic volum e. T h e nucleus is composed o f A particles ( A is the mass
number) called nucleons, o f which Z are protons {Z is the atomic number), each o f
charge + e , and N ( = A — Z ) are neutrons, which have no electric charge. T h e re ­
fore the nucleus possesses a positive charge o f + Z e . T h e number o f electrons in an y
atom is equal to the number o f protons (th a t is, Z o f them ) and th erefore an atom
is an electrically neutral system. H ow ever, in certain instances an atom m ay gain
or lose some electrons, so th at it becomes n egatively or p ositively charged; in this
case it is called an ion. T h e mass o f the nucleon is about 1850 tim es the electron
mass. Thus the mass o f an atom is practically equal to that o f its nucleus.
H ow ever, the Z electrons o f an atom are responsible for m ost o f the atom ic
properties which are reflected in the properties o f m atter in bulk, such as the
elastic and electrom agnetic properties of different materials. E lectrom agn etic
interactions between electrons and nuclei o f different atom s play the basic role in
the binding togeth er o f atom s to form molecules, in chemical reactions, and in
practically all the properties o f m atter in bulk.
W e can explain the m otion o f the electrons around the nucleus if w e consider
on ly the electrom agnetic interactions between the electrons and the com ponents
o f the nucleus (protons and neutrons). Since electrom agnetic interactions are w ell
understood, it has been possible to d evelop an accurate description o f the electronic
m otion. T h e corresponding problem fo r the nucleus, on the other hand, is m ore
complex, since other interactions enter which are not so w ell understood. W hen w e
analyze electronic m otion, we must use the m ethods o f quantum mechanics dis­
cussed in the previous chapter.
In this chapter we shall discuss the properties o f atom s and ions having just one
electron (o f which the sim plest is the hydrogen ato m ) and in the follow ing chapter
w e shall consider the problem o f m any-electron atoms. T h e one-electron atom w ill
help us to understand the basic problem s related to atom ic structure.

3.2 T he H y d ro g en A to m
T h e sim plest o f all atom s is the hydrogen atom. Its nucleus is composed o f on ly one
particle, a proton, so that it has /1 = 1 and Z = I. Around the proton, a single
electron moves. So th at our calculation w ill be applicable to other atom s w e shall
assume, however, th at the nucleus contains Z protons w ith a to ta l p ositive charge
equal to + Z e (F ig . 3 -1 ). A t this m om ent w e shall make tw o approxim ations. First,
we shall consider the nucleus to be a t rest in an inertial system. T h is is a reasonable
assumption because the nucleus, being m ore massive than the electron, practically
coincides w ith the center o f mass o f the atom , which certainly is a t rest in an inertial
system so lon g as no external forces act on the atom. Second, w e shall assume that
the electric field o f the nucleus is th at o f a point charge. T h is is also reasonable,
HO Atoms with one electron (.3.2

since the nucleus has a v e ry small size (abou t IO-14 m ), com pared w ith the average
distance o f the electron from the nucleus (abou t IO-10 m ). H ow ever, in a m ore
refined analysis, the size and shape o f the nucleus would h a ve to be taken into
account.

Electron

Fig. 3-1. An electron moving around a nucleus.

T h e m otion o f the electron relative to the nucleus is determ ined b y the coulomb
interaction between the two. T h is interaction is expressed b y an a ttra c tiv e inverse-
square central force acting on the electron, given b y

*■ = - 4 ^ -

T h e poten tial energy o f the electron-nucleus system is then

- - Π 5 Γ <3-2’

H ow ever, since we must an alyze the m otion o f the electron b y means o f quantum
mechanics, w e cannot solve the problem b y ap p lyin g the N ew ton ian equation o f
m otion F = d p /(It) instead w e must set up Schrodinger’s equation for m otion,
w ith a potential energy given b y E q. (3.2). Because the electronic m otion is three-
dimensional, w e must use E q. (2.9). T h is results in a Schrodinger equation o f the
form

_ * (€ * + ψ = E i (3.3)
2 TO V d x 2 dy2 d z 2/ 4 7re0r ψ ψ K '

T h e solution o f this equation is an arduous m athem atical problem , for which the
student is not y e t properly equipped. F o r the present, we shall lim it ourselves to a
consideration o f the energy o f the stationary states. W e shall discuss the w ave
functions φ in Section 3.4.
L e t us introduce a constant, called Rydberg's constant, defined b y *

Rx - -^ 4 - = 1.0974 X IO7 m - 1 . (3.4)

S f lh 3C

* The reason for the subscript co will be apparent later on.

3.2) The hydrogen atom 111

T h e possible energy levels for the sta­

tionary bound states o f the electron,
which w e obtain from E q. (3.3), are
given b y the expression
1(1
R xIicZ 2
E n= - 13.0 eV
n2
2.180 X K T '20
J, (3.5)
Tl2

where n = I , 2, 3, . . . (p ositive inte­

30
gers). Som etim es it is more convenient
to express the result in electron volts.
M a k in g the proper changes in the
•10
units, w e get cV

13.607/i
En = ~ eV. (3.6) 50

N o te th at the values o f the total energy 54.4 c V

are negative. T h is is in agreem ent w ith (id
the classical result for m otion under an
inverse-square force when the orb it is
I
elliptical or bound. T h e zero p oin t o f I in
the en ergy is assigned to the state in
which th e tw o particles (electron and
nucleus) are a t rest at an infinite dis­ 120
tance apart. T h erefo re, E q. (3.6) is
122.5 cV
equ ivalent to the energy, in classical
mechanics, for the m otion o f particles in
elliptical orbits; how ever, let us remind F ig. 3-2. Some energy levels of II, H e + ,
the reader that one does not talk about and L i2+.
precise orbits in quantum mechanics.
Expression (3.6) applies to an y atom which has a single electron. Thus it holds
for hydrogen (Z = I ) and its isotopes, deuterium (/I = 2, Z = I ) and tritium
(A = 3, Z = I ) ; for singly ionized helium, I I e + (a helium atom th at has lost one
o f its tw o electrons, Z = 2 ); for dou bly ionized lithium L i 2+ (a lithium atom that
has lost tw o o f its three electrons, Z = 3 ), etc. F igu re 3-2 shows the corresponding
theoretical energy levels. T h e app rop riate values o f n are indicated for some levels
in each series.
N o te that some levels in Fig. 3-2 arc coincident. F o r example, hydrogen levels
coincide respectively w ith the levels o f H c + which have n = 2, 4, 6, . . . and also
with those o f L i 2+, which have n = 3, 6, 9 ,. . . T h e reason for this is th at some
common factors are canceled in E q . (3.6) due to the respective values o f Z . The
coincidence, however, does not occur exactly in nature. T h e nucleus is not at rest
in an inertial fram e; rather the nucleus and the electron rotate about th eir center
112 Alomswilhoneeleclron (3.2

T A B L E 3-1 K yd b erg’ s C onstant

(R x = 10,973,731 m ” 1)

Atom Z A R, m 1

Hydrogen (H ) I I 10,967,758
Deuterium (D ) I 2 10,970,742
Tritium (T ) I 3 10,971,735
Helium (H e +) 2 4 10,972,227
Lithium (L i2+) 3 7 10,972,880
Beryllium (B e3+) 4 9 10,973,070

o f mass. H ow ever, we can an alyze the relative m otion o f the electron and the
nucleus b y substituting, in E q. (3.4), the reduced mass o f the electron-nucleus
system for the electron mass. G iv e n th a t M is the mass o f the nucleus, then the
reduced mass o f the atom is*

m eM _ mB
^ 7ne -j- Jl/ I Έ Jl/

T h erefo re in E q. (3.5) we m ust replace R y d b c rg ’s constant R x b y

R = = R v — =* R - , 1 /M ) - (3.7)
8 ίοΛ c m« V 1 + m t/ M )

so th at the energy levels are g iven b y E = — R h c Z 2 /n2. T h e value o f R for sev­

eral nuclei is given in T a b le 3-1. O bviou sly R x corresponds to the case in which
the nucleus has infinite mass (Jl/ = c c ), and this explains the reason for the sub­
script on the sym bol.
So far w e h ave considered on ly states o f n egative energy, or bound stales. The
states o f positive energy, which in a classical description correspond to hyperbolic
orbits, are unbound slates, in which an electron w ith enough kinetic energy
approaches the nucleus from a great distance and, a fter being d eviated from its
straight-line m otion b y its coulom b interaction w ith the nucleus, recedes again
toward in fin ity. A s explained in Section 2.7, positive energy states are not quan­
tized, since the initial kinetic energy m ay have an y arb itra ry value and thus they
form a continuum o f states.

E X A M P L E 3.1. Semiclassical derivation of the expression for the energy levels of

hydrogen.

S o lu tio n : We may justify Eq. (3.5) for the stationary states of the hydrogenlike atoms
just as, at the end of Section 2.5, we justified the energy levels for a particle moving in a
potential box by using concepts derived from our knowledge of standing waves. Let us
suppose that the electron describes a circular orbit, as shown in Fig. 3-3. Its momentum p
is constant for a circular orbit. In order that the orbit correspond to a stationary state,

* See, for example, Fundamental Unieersily Physics, Volume I, Section 9.3.

3.2) Thehyilrogenalom 113

Fig. 3-3. Standing waves on a circle.

it seems logical that it must be able to sustain standing waves of wavelength λ = Ιι/ρ.
We can see from Fig. 3-3 that this requires that the length of the orbit be equal to an
integral multiple of λ; that is, 2 irr = n\ - nh/p or

rp = ηΙι/2π. (3.8)

Noting that rp is the angular momentum of the electron, we see that the stationary states
are those for which the angular momentum is an integral multiple of Λ = Ιι/2π. Since
p = mtv, we may also write Eq. (3.8) as

mcvr = nh/2v. (3.9)

On the other hand, the equation of motion for the electron requires that I·' = mcv2 /r,
where F is the centripetal force. But in the case of an electron moving about a nucleus,
the centripetal force is the coulomb force given by Eq. (3.1). Therefore

mcV2 Ze 2 2 Ze 2 .„ . . .
= 5 or OicV = - ------- (3.10)
r 4ir<or^ 47r<or

When we eliminate e between Eqs. (3.9) and (3.10), we have

2 2 2
n h to n . .
r = = -=■ ao, (3.11)
TrmcAez A
where
,2
O0 = ---- % = 5.2917 X IO-11 m (3.12)

is called the Bohr radius. Expression (3.11) gives the radii of the allowed circular orbits
and the Bohr radius, ao, is the “ radius” of the ground-state orbit (n = I ) in hydrogen
(2 = I).
When we use Eq. (3.2) for the potential energy of the electron-nueleus system, we may
express the energy of the electron in a circular orbit as:

7 ~
E = E k + E p = ^meV2 — -------
47Tior
Uh Atoms with one electron

Hence, if we use Eq. (3.10) to eliminate mev2, we obtain

* - - 5 5 5 5 · <3· ' 3>

Introducing the value of r as given by Eq. (3.11), we have

,, m,.e%
Z~ R J ic Z 2
O 2 .2 2 «2 ’
8«o « n

which agrees with Eqs. (3.4) and (3.6). However, a word of caution concerning our
derivation: Besides being applicable only to circular orbits, it all depends on the validity
of Eq. (3.8), which we shall discuss in more detail later (Section 3.4). On the other hand,
the concept of orbit must be considered here as applying to the region in which the electron
is most likely to be found, and Eq. (3.11) is only an indication of the magnitude of the
region in which the electron moves most of the time, and thus of the size of the atom.
Combining Eqs. (3.9; and (3.11), we find that the velocity of the electron in a stationary
orbit is
nh HZ 21.9 X IO5Z _1
" — — — 111 S .
27rmer ‘2irm,.non n

W e must consider this result as indicating only the order of magnitude of the velocity
of the electron. N ote that the velocity decreases when the energy increases (larger value
of n ). Also we have that v/c ~ 7 X IO-3 Z/n, and thus v « c, except for large values of Z
and small values of n. Hence relativistic corrections are not very important except when
great accuracy is desired. However, these corrections are very important from the
theoretical point of view.

E X A M P L E 3.2. Estimate the magnitude of the correction term in Eq. (3.7), due to the
nuclear motion, for the energy of the stationary states of the lightest atoms; that is,
H, D, T , H e+ , and L i 2+.

S o lu tio n : Since m j M is a very small quantity, we may, by using the approximation

( I + x ) _ l = I — x + ■ ■ · , write Eq. (3.7) as

Λ = / ? „ ( ΐ - ^ ) or AR = R - Rx = - j j Rx .

The mass of an atom of mass number .1 can be written, to a good approximation, as

M = 1.67 X IO - 27A kg and me = 9.11 X IO" 31 kg. Thus m J M = 5.45 X 1 0 ~ V A .
Therefore since the energy is proportional to R, we may write

AE me nico/ 5.45 X 10 ~ ^
— HK) %,

where A E is the change in energy from the value given in Eq. (3.5). The results for the
lightest elements are indicated in Table 3-2.
The fact that A E / E is different for H, D, and T means that the energy levels for these
three hydrogen isotopes are slightly displaced, resulting in what is called an isolopic effect.
Similarly, the even levels of H e+ do not exactly coincide with those of II. It was this
minor difference that led to the discovery of helium by Frankland and Lockyer when they
analyzed the solar spectrum in 1868.
3.3) The spectrum of hydrogen 115

T A B L E 3-2 E nergy Correction s W h en N u c le a r M o tio n Is

Considered

Atom H I) T Ilc + L i2+

Λ I 2 3 4 7

( m ./M ) X IO4 5.45 2.75 1.82 1.36 0.78

- (A E / E ), % 0.0545 0.0275 0.0182 0.0136 0.0078

3.Ii T h v Spvvlrunt o f H yifrogvn

A s we saw in F ig. 3-2, the energy o f the stationary states increases with the quan­
tum number n . T h e difference in energy between the levels corresponding to Ti1
and Ti2 (w ith n 2 > n t ) for a hydrogenlike ion is

*, - , (- ^ W 7 U - 4

W h en w e ap p ly B oh r’s condition, v = ( E 2 — E 1)/Ii (E q. 1.29), and neglect recoil

effects, the frequency o f the electrom agnetic radiation em itted or absorbed by the
atom in a transition between states corresponding to Ti1 and n 2 is

„ = E i~ El = R cZ2 ( \ - K

V - " 6
= 3.2899 X IO 15 Z 2 ( \ \ ) IIz . (3.14)
«I Tl2J

Spectroscopists sometimes prefer to use the wave number v = v/c = I /λ, rather
than the frequ ency.* T h e ir reasoning is th at spectroscopic measurements usually
determ ine wavelength and not frequency. T h e w ave number in the M K S C system
is given in m —*, although the m ost common unit is cm - 1 . In this case the ab ove
equation becomes

P = RZ2 l \ - ^ = 1.0974 X IO 5 Z 2 I - - c m - 1.
\«i n\j X n 21 Ti2
2J

T h is expression (o r the preceding one) is called B alm er’s form u la , and is applicable
only to hydrogcnlike atoms. Since in a spectroscope (either prism or gratin g), each
transition appears as a line (which is the im age o f the slit), the spectrum is called a
lin e S])ectrum, and frequently the words line and transition are used as synonyms.

* The wave number v gives the number of wavelengths in one unit of length, and it should
not be confused with the wave number k = 2?τ/λ, which is associated with a particle, and
W'hich was defined in Section 1.10.
116 Atoms with one electron (3.3

Energy, eV
Continuum
,----------

1111 - 0 .5 4
W Pfund series
- 0 .8 5
Brackett series
- 1 .5 1
Paschen
series

LI Balmer
series
- - 3 .3 9

Lyman j

T h e hydrogen spectrum ( Z = I ) (and sim ilarly for the spectra o f other atom s) is
classified in terms o f series, each series form ed b y transitions th at h ave the low est
energy level in common. F igure 3-4 represents the follow in g hydrogen series:

(1 ) L ym an series: Ui = I, n 2 = 2, 3, 4, . . .
(2 ) B alm er series: ηχ = 2, n 2 = 3, 4, . . .
(3 ) Paschen series: = 3, n 2 = 4, 5, . . .
(4 ) B rack ett series: Πχ = 4, n 2 = 5, 6, . . .
(5 ) Pfund series: Ti1 = 5, n 2 = 6, 7, . . .

T h e B alm er series, which is m ostly in the visible region, is easily observed w ith a
com m on spectroscope. T h e L y m a n series falls ih the u ltraviolet region and the
others in the infrared. T h e transitions indicated in F ig. 3-4 correspond to the
emission spectrum ; the reverse transitions take place in the absorption spectrum.
3A) Quantization of angular momentum 117

H istorically, the problem o f explaining the line spectra o f hydrogen and other
elements was w h at caused the first application o f the quantum th eory to the atom.
T h e Swiss m athem atician J. B alm er (1825-1898), long before the ad ven t o f the
quantum theory, em pirically obtained form ula (3.14) in 1885, w ith ou t any th eoreti­
cal explanation related to atom ic structure. In 1913 the Danish physicist N iels
Bohr, then at C am bridge U n iversity, d erived E q. (3.14) b y introducing, for the
first tim e, the concept o f stationary states. Since quantum mechanics had not y e t
been form ulated, B o h r’s m ethod consisted o f a series o f ad hoc assumptions closely
resem bling the calculations m ade in E xam ple 3.1.

E X A M P L E 3.3. Determine the first excitation potential and the ionization energy of
hydrogen.

S o lu tio n : As we explained when we discussed the Franck-Hertz experiment in Section 1.8,

the first excitation potential is the energy required to take an atom from its ground
state to its first (or lowest-lying) excited state. These states in hydrogenlike atoms
correspond, respectively, to n = I and n = 2. Setting n = I and n = 2 in Eq. (3.6)
with Z = I, we have E i = — 13.6 eV and E 2 = — 3.4 eV. Thus the energy required to
excite the atom from the ground state to the first excited state is E 2 — E 1 = 10.2 eV.
If a hydrogen atom is carried to its first excited state by an inelastic electron collision, as
happens in a gas discharge tube, it returns to the ground state by emitting radiation of
frequency
v = (E 2 - E i)/ h = 2.47 X IO15 Hz

or wavelength

λ = 1.216 X I O " 7 m,

which in this case falls in the ultraviolet region. The ionization energy is the energy
required to take the electron from the ground state (n = I) to the state of zero energy
(n = co), and thus is equal to — E 1 = 13.6 eY. Ionization may result from either an
inelastic collision of the hydrogen atom with an electron or another charged particle, with
another atom, or from the atom’s absorbing a photon having a frequency equal to or
larger than 3.29 X IO 1 0 H z or a wavelength equal to or shorter than 9.12 X IO-8 m.

3.4 Quantization o f A n g u la r M o m e n tu m
So far w e have seen th at the energy o f an atom ic system is quantized. W e must
explore the possibility th at some other physical quantities are also quantized; i.e.,
restricted to on ly certain values for the system. W e noted at the end o f Section 2.5
that the m om entum o f a particle in a p oten tial box is also quantized. In m ost
examples in C hapter 2 the m om entum and/or the energy were constants o f the
m otion; i.e., quantities whose value does not change during the m otion o f the
particle. I t is reasonable then to inquire w hether or not other constants o f
the m otion are quantized.
W e know th at for m otion under central forces, the angular m om entum L = r x p
relative to the center o f force is a constant o f the m otion. In quantum mechanics
this is also true. A careful theoretical and experim ental analysis shows th at the
118 Atoms with one electron

T A B L E 3-3 D e sig n alio n o f A n g u la r M o m e n tu m States an d

E ssential D egeneraey fo r M o tio n U n d e r C en tral
Forces

Angular momentum, I 0 I 2 3 4 5

Symbol s P d f g h

Degeneracy, g = 21 + I I 3 5 7 9 11

angular mom entum is qu antized; i.e., it m ay have on ly discrete values. I t can be

shown (see E xam p le 3.4) th at the m agnitude of the angular m om entum is charac­
terized by the values

L 2 = Z ( Z - M ) A 21 (3.15)

w here I = 0, I, 2, 3, . . . is a positive integer. H ow ever, in hydrogenlike atom s the

values o f I for each energy level are lim ited b y the values o f n corresponding to the
energy level, and the m axim um value o f Z is w — I. T h erefore

in a coulomb field, f o r each value o f n, specifying an energy level, there

are n distinct values o f the angular momentum fro m I = O to I = n — I.

I t is custom ary to designate the possible values o f I by means o f letters, according

to the scheme o f T a b le 3-3. T h erefo re for n = I we have I = 0 or s; fo r n = 2 we
have I = 0 and I or s and p. For M = 3, it is I = 0, I, and 2 or s, p, and d, etc.
In a central field d ifferent from the coulomb field the values o f I associated w ith
each energy level are also different. F o r example, in the case o f a three-dimensional
oscillator the potential energy is E p = Jfcr2. T h e possible energy levels are E =
(n + |-)Λω (see E q. 2.22), and fo r each n the I values are η, n — 2, n — 4, . . . ,
I or 0. T h e n for n = 0 w e h ave I = 0 or s; for n = I, I = I o r p ; for n = 2,
I = 0 and 2 or s and d, and so on.
In addition to its lim itation w ith regard to its
m agnitude, experim ental eviden ce (to be discussed Z
later) indicates th at the angular m om entum is re­
stricted in direction, a situation called space quan­
tization. T h is means th at the angle L makes w ith the
Z -axis (F ig . 3 -5 ) is not arb itra ry; in other words, it
can be shown (see E xam ple 3.4) th at the values o f the
com ponent L z are quantized and given by

Lz = m ih, (3.1C)

where m i = 0, ± 1, ± 2 , ± 3 ........... ± Z ; th at is, m i is a

positive or negative integer from 0 to I. T h e quantum
number mj cannot be larger than I because L z would
then be larger than \L\, which is impossible. T h erefore
we conclude th at:
 3A ) Quanlization of angular momentum 119

Z Z

Fig. 3-6. Space quantization illustrated for I = I and 1 = 2.

f o r each value o f the angular mom entum , there are 21 + I values o f mi

or 21 + I different orientations o f L .
I

Figure 3-6 illustrates this situation for I = I and I = 2. T h e q u a n tity g = 21 + I

is called the essential degeneracy o f the angular mom entum state. I t can be proved
that this degeneracy is a consequence o f the spherical sym m etry o f the m otion
under a central force. T h e values o f g for a few angular m om entum values are given
in T a b le 3-3.
In classical mechanics the angular m om entum under a central force is constant
I in m agnitude and direction. H ow ever, in quantum mechanics, the m agnitude o f
the angular m om entum is g ive n b y E q. (3.15) and o f one o f its com ponents by
E q. (3.16). Buti to specify the direction o f the angular m omentum, w e need to
know the tw o other components, L e and L il. A detailed analysis, which w ill not
be reproduced here because o f its m athem atical com plexity, shows th at

it is impossible to know, exactly, more than one component o f the angular

momentum.

Therefore, i f w e know L z, our know ledge o f L 1 and L y is at best w ith in the un­
certainties A L 1 and A L y, which satisfy the uncertainty relation

A L r A L y ^ \ h L z.
120 Atoms with one electron {3Λ

T h is relation is sim ilar to the uncertainty relations for position and mom entum
(E q . 1.48), and for energy and tim e (E q . 1.49). In other words,

in quantum mechanics, it is impossible to precisely determine the

direction o f the angular momentum.

Since w e can know on ly |L| and L 1, w e m ay picture the angular mom entum vector
L in Fig. 3 -5 as precessing around the Z-axis, a t a constant angle Θ.
From this discussion we m ay conclude
th at the energy levels o f hydrogen like
„ / = () / -I /= 2 I=3 I= 4
atoms are som ewhat m ore com plex than /M----
the sim ple picture im plied in E q. (3.6)
and Fig. 3-2. In a coulom b field each
energy level, corresponding to a given n,
G ------- ------- ------- -------
contains n different angular m om entum
states, all w ith the same energy and w ith
I ranging from zero to n — I (this is
shown in Fig. 3 -7 ). T hese levels are in­
dicated b y ns, np, nd, etc. (T h is result
agrees w ith the classical description of
m otion under an inverse-squarc force, for
which the energy is independent o f the
angular m om entum , although the eccen­
tric ity o f the elliptical orbits depends on
the angular m om entum .) In a m ore re­
fined th eory o f one-electron atom s which
takes into account other effects (such as
relativistic corrections), the different an­
gular m om entum states corresponding to
the same n appear w ith different energies.

Fig. 3-7. T ransitions among different an­

gular momentum states.

I f the force is not inverse-square, those levels which have the same value o f n but
different angular m om enta (i.e., levels ns, np, nd, etc.) do not necessarily all have
the same energy. Thus under central forces, the energy depends in general on n
and I, but it cannot depend on m i, since in a central field o f force the orientation o f
the orbit is irrelevant.
T h e fact that each level in a hvdrogenlike atom is composed o f several angular
momentum states is, however, im portant from the point o f v iew o f the transitions.
F o r m otion in a central-force potential, the selection rules for electric-dipole transi­
tions are

Al = ±1, A m i — 0, ± 1 . (3.17)
3.5) One-electron wave functions under central forces 121

These selection rules are imposed b y the law o f conservation o f angular momentum,
since the em itted or absorbed photon carries angular m om entum ; therefore the
angular m om entum o f the atom must change to compensate for the angular
momentum carried by the em itted or absorbed photon. T h e law o f conservation
o f angular mom entum and the quantum rule for addition o f angular m om enta (see
Section 3.8) would allow Δ/ = 0, ± 1 . H ow ever, the p arity o f the w ave functions
in a central potential (to be discussed in Section 3.5) forbids the possibility that
Al = 0.
T h e selection rules (3.17) require th at transitions occur on ly between angular
mom entum states in adjacent columns o f Fig. 3- 7. Some o f these possible transitions
have been indicated. N o te that, according to these rules, the state 2s cannot change
into state Is, which is the on ly low er-lyin g level available. F or th at reason the state
2s is called a melastable slate. T h e rules (3.17) are valid for electric-dipole transi­
tions, which are the most probable. F or other transitions, such as m agnetic-dipole
or electric-quadrupole transitions, the selection rules are d ifferent; these transitions
have a much low er p robability than electric-dipole transitions. F or this reason, in
atom ic spectra, usually on ly electric-dipole transitions are taken into account.
L e t us now com m ent on Eq, (3.8). N o tin g that for a circular orbit rp is the
angular momentum L , we see that Eq. (.3.8) reads L - nh. Hut this result dis­
agrees w ith E q. (3.15), which is L = \ / l(l + I ) Λ. H ence the sim ple and in tu itive
model used in E xam ple 3.1 for obtaining E q. (3.8) is incorrect (although the result
obtained is correct). T h is again warns the student th at it is not possible, unless one
takes great care, to extrapolate w a v e concepts when they arc applied to quantum
mechanics. In this case of angular momentum, the discrepancy is due to the fact
that it is im possible to confine the electron w aves to a strict circular path. H ow ever,
setting I = n — I in Eq. (3.15), we get

L 2 — {n — \)nh2 = (n 2 — n )h 2.

I f n is large w e m ay approxim ate this expression by w ritin g L 2 ■ n2h2 or L = nh,

which agrees w ith E q. (3.8). Thus I — n — I w ith n large approxim ates the
classical circular orbits. T h is is an illustration o f B oh r’s correspondence principle,
which states that for large quantum numbers the quantum description approaches
the classical description.

•I..* O n o -E lvvtro n W a v v Funvtions F n d v r F vn trn l Forvvs

T h e w ave function ψ (χ ,ρ ,ζ ) for hydrogenlikc atoms is obtained by solving
Schrodinger’s equation, Eq. (3.3). T h e potential energy which appears in that
equation, E p = - -Z e 2/ Atvt nr, corresponds to a central force. W c m ay expect that
the w ave functions o f all ccntral-force problem s [i.e., problem s in which the poten­
tial energy is only a function o f the distance and therefore has the form E p{r)\ have
a certain sim ilarity.
Because o f the spherical sym m etry o f the potential energy, w e can sim plify the
discussion o f central-forcc problem s by using the spherical coordinates r, 9, φ
122 Atoms with one electron (.3.5

F ig. 3-8. Spherical coordinates. Fig. 3-9. Angular wave function for
s-states (1 = 0).

(F ig. 3 -8 ). W e can show that the w a ve function for a single electron in a central
field can be w ritten as a product o f tw o factors, one that depends on the distance
o f the electron from the origin and another that depends on the orientation o f the
position ve cto r r, given b y the angles 9 and φ. Thus w e m ay w rite the w ave
function as

φ {τ, θ, φ) = R (r )Y (9 , Φ).

T h e radial p art R ( r ) depends on the particular form o f the potential energy E p(r )
corresponding to the force acting on the electron. H ow ever, since the angular part
Y (9, φ ) is a consequence o f the spherical sym m etry o f the central force, it is inde­
pendent o f the particular form o f the potential energy E p(r ). In other words, the
angular f unctions Y (9, φ ) are the same f o r all central-force problems.
W e shall not an alyze how to obtain the w ave functions, although it is a straigh t­
forw ard m athem atical problem (see E xam ple 3.4). Instead we shall discuss the
m ost im portant properties o f the w a v e functions.

I n a central-force problem the angular part o f the wave fu n ction is

determined entirely bg the magnitude and the Z-com ponent o f the angular
momentum o f the electron.

T h e m agnit ude o f the angular mom entum is determ ined by the quantum number I
and the Z-com ponent or orientation is determ ined b y m/. F o r th at reason the
angular functions corresponding to specific values o f L 2 and L 2 w ill be designated
as Y im,(9, Φ). M athem aticians call these functions spherical harmonics.
T a b le 3-4 gives the angular functions F j mj for Z = O, I, and 2. T h is is the form
which is applicable to m ost physical problems. T a b le 3 -5 gives the angular func­
tions in a form m ore suitable to the discussion o f m olecular binding. T h e functions
in T a b le 3-5 do not belong to a particular value o f m i, but o f m 'j o r |m;|, and they
correspond to L 2 and L 2 instead o f L 2.
3.5) One-electron wave functions under central forces 123

T A B L E 3-4 A n g u la r F u n ction s C orresp on ding

to L 2 an d L1

I mt Angular function

0 0 lo o = l/ V lir

0 T io = V 3/47r cos 0
I ✓
±1 l ' i ± i = zF V 3 / 8 r sin Θ e * 1*

0 T 20 = 5/47Γ (3 cos2 Θ — I)

2 ±1 l*2± i = T V lS / S jr sin Θ cos Θ e*

±2 I"2±2 — 4\/15/2π sin2 Θ e r '2*

T A B L E 3-3 A n g u la r F u n ction s C o rresp on din g

to L - an d L j

I M Angular function

0 0 S = l/\/4ir

0 ps = ν/3/4τΓ cos Θ

P i = V3/4ir sin Θ cos φ

I
p„ = V3/4tt sin Θ sin φ

0 d 3,2_ r* = \/5/\6π (3 cos2 Θ — I)

2 d „ = ν ' 1S/47T sin Θ cos Θ cos φ

I
Aus = V 15/47Γ sin Θ cos Θ sin φ

2 dx2_v2 = \/\5/4ir sin2 Θ cos 2φ

d iV = vT5/4ir sin2 Θ sin 2φ

From T a b le 3 -5 w e can see that for I = 0 (o r s-states), the on ly w a v e function is

independent o f the angles; th at is, s-states are spherically sym vielric. W e can see
this in the polar diagram o f Fig. 3-9, where the value o f the s-function fo r each
direction ( θ, φ ) is indicated by the length o f a line from the origin. T h e locus o f the
end points results in a spherical surface. T h is result is understandable because, if
the angular mom entum is zero, there is no preferred orientation o f the electron’s
orbit.
For f = I (o r p-states), there are three angular functions, representing the three
possible orientations o f the angular m om entum o r the three values o f m i = 0, dbl.
T a b le 3-5 designates them as pz, pv, and p, and they are shown in the polar dia­
grams o f Fig. 3-10. T hese functions correspond to a preferred m otion o f the
12b Atoms with one electron (3.5

Fig. 3-10. Angular wave functions for p-states (I = I).

“ 3,2-r>

Fig. 3-11. Angular wave functions for d-states (i = 2).

electron along each o f the coordinate axes, a result th at is v e ry im portant for

describing chem ical binding.
For I = 2 (o r d-states), there are five d ifferent angular functions. T h e angular
distribution o f these states is m ore com plex, as w e can see from the polar diagram s
o f Fig. 3-11, which represent the d-functions o f T a b le 3-5. F o r larger values o f I,
the situation becomes even m ore complex.

I .
3.5) One-electron wave functions under central forces 125

T A B L E 3-6 R adial W av e F u n ction s o f H ydrogcnlike

A to m s

n I R n M (p = 2Zr/nad)

^3/2
e-,/2
I O Λ ιο Μ = 2 ( -
\a0/
3/2
O R2 0 O) = — ) (2 - p ie - ”12
2\/2 W
2
W ' 2 —p/2
I
* » < - > - * 7 8 1 VaO/ PB
3/2
O (6 - 6p + p2)e_,>/2
* » < ' > - 9 7 ! I' £ )

3 I
* ■ ■ < '> - m I' S r * - * - -
v 3/2
2 ) P*e- " 2
* “ <'> - 9 7 3 0 ( C

A n im portant p rop erty o f the angular functions Y i mi is th at they have a parity

equal to ( — 1)(. T h a t is, for I = 0, 2, 4 , . . . , even integer, the functions Y imi have
the same value and sign a t points sym m etrically situated rela tive to the origin of
coordinates, and thus are even functions, while for Z = I , 3, 5 ,. . . , odd integer,
the functions Y im. have the same value but opposite signs a t sym m etric points,
and are odd functions. I t can be shown th at for electric-dipole transitions the initial
and final states must have opposite parities, and therefore these states cannot have
the same value o f I. F o r that reason the value Δ/ = O is im possible for these
transitions, as previously indicated in connection with E q. (3.17).
T h e radial part R ( r ) o f the w ave function ψ(ν, Ο, φ) depends on the energy and
the m agnitude o f the angular mom entum , but n ot on its orientation. W e can under­
stand this because the spherical sym m etry o f a central field indicates th at the radial
distribution o f the electron’s m otion m ust be independent o f the orientation o f its
angular m om entum ; th at is, it must be independent o f the value o f Otj. T h is is the
quantum analog o f the classical result th at the energy and the m agnitude o f the
angular m om entum determ ine the “s iz e ” o f the orbit. T h erefore the radial function
depends on the quantum number n associated w ith the energy, and on I, but not on
m i. Thus these radial functions are w ritte n as /?„/(>'), and the to ta l w a v e functions
become
t n lm f a θ, φ) = R n l(r )Y im,ie, φ ). (3.18)

T a b le 3 -6 g ives the radial functions corresponding to the first three energy levels
o f hydrogenlike atoms. T hese functions are shown in Fig. 3-12. T h e dashed line in
each case indicates the classical radius o f the orbit, in accordance w ith E q. (3.11).
i26 Aloms with one electron (,3.5

n-1

r, A

F ig. 3-12. Radial wave functions of hydrogen for n = 1,2, and 3. The ordinate of the
curves in each case is [ff„i(r ) ra-3/2] X IO-8 .

»1 = 1 40 - n - 2 40

/\ , =0
20 - 20

I Γ '- J
0
4 8 4 i 8 12

/=1
20

I I -----I
4 ; 8 12

/= 2
20

_____ I I I — —L____I
4 : 8 12
«3
r, Λ

Fig. 3-13. R ad ialp ro b a b ilityd istrib u tion in h yd rog en forn = 1,2, and 3. Theordinate
in each case is \r2R ni(r ) m -1 ) X IO-15.
3.5) One-electron wave functions under central forces 127

W e can see that, although the electron is m ost likely to be found within the
classical radius o f the orbit, it m ay also be found a t larger distances. T h e p rob ab ility
o f finding the electron within a spherical shell o f radii r and r - f dr, regardless o f its
angular position, is proportional to r 2[/?„j(r) ] 2 (see Problem 3.25). Figure 3-13
shows these probabilities.
One interesting peculiarity, easily appreciated by looking a t F ig. 3-12, is that the
radial functions for s-electrons arc rela tively large for small r. W e say th at the
s-electrons describe penetrating orbits reaching v e ry close to the nucleus. T h e
p-electrotis are less penetrating, the d-electrons even less so, and so on for higher
values o f the angular m omentum. T h is is easy to understand if w e consider that
(in both classical and quantum mechanics) the radial m otion under a central force
corresponds to an effective potential

(3.19)

where E p( r ) is the potential energy o f the central force (th e coulomb potential in the
case o f an electron) and L 2/ 2 m r2 is called the centrifugal potential (see E xam ple 3.5).
F o r s-states w e have I = 0 and there is no centrifugal potential, so th at E p,cff =
Ep. T h u s a bound s-electron w ith negative energy E (F ig . 3-14a) can classically
m ove between 0 and A , and therefore has access to the origin o f coordinates. T h e
shape o f the radial part o f the w ave function must then be as shown a t the bottom
o f the figure. (T h e number o f oscillations o f the w ave function depends on the
energy.) B u t for other values o f the angular m omentum, the shape o f the effective
potential is as shown in Fig. 3 -1 4 (b ). T h erefo re an electron o f energy E must m ove
classically between B and C. W e translate this into quantum -m echanical language
b y statin g that the w ave function must decrease v e ry rapidly outside the classical
lim its o f m otion, and must therefore be v e ry small near the origin. T h e larger the
angular m omentum, the further the w a v e function is pushed aw ay from the origin
and the less “p en etratin g” is the orbit.
T h is characteristic o f electron m otion is reflected in m any im portant properties
o f the atom . F o r example, s-electrons are v e ry sensitive to the shape and internal
structure o f the nucleus, while electrons w ith larger angular m om entum are much
less sensitive to nuclear shape and structure.

E X A M P L E 3.4. Analysis of angular momentum operators and proper functions.

S o lu tio n : W c recall from Table 2-4, Section 2.12, that the angular momentum operator
is given by
Uv u.
I - — ih r X V = — ih x y *
d/dx d/dy d/dz

from which we conclude that the Z-component is

(3.20)
l ‘ “ - ih { Xf y ~ V£ ) '
H28 Atoms with one electron (3.5

^Centrifugal potential—/!/rO/r2
\
\
\
v
s

s-eleetron ( I = U)

(a) (b)

F ig . 3-14. Effective potential and radial wave function for I = Oand I t*· 0 for motion
under a central force.

with similar expressions for L1 and L„. It is more convenient to express Ls in terms of
spherical coordinates. N oting from Fig. 3-8 that

x — T sin 0 cos φ, y — T sin 0 sin φ , z = r cos Θ,

we have that
d dx d , dy d dz d
dφ dφ dx ' 3φ dy d φ dz

But dx/dφ = — r sin 0 sin φ = — y,dtι/ΰφ = r sin 0 cos φ = x, and dz/ΰφ = 0. Therefore

0 d , d
dφ 1J d x X dy’
3.5) One-electron wave functions under central forces 129

and the operator L2 can be written in the form

L' = - i A j ; · (3-21)

I t can be shown that this relation is absolutely general and that the quantum operator
corresponding to the component of the angular momentum along any direction is given by
—ih d/Οφ, where φ is an angle measured around the direction. The proper equation,
according to Eq. (2.48), is L.Φ - Φ, where Φ (φ) is the properfunction and L 1 the
proper value. Therefore, using Eq. (3.21) for L1, we obtain

- I ·,r t - = LT 1Φ
τ, or 5Φ · ;,Φ
— = ιη * .
ϋφ οφ

where we have set nij = L J h or L 1 = m/A. The solution of this equation is Φ = CeimIφ
where C is the normalization constant. Since the same point of space is represented by φ
and by φ -f- 2π, it is necessary that Φ(φ) = Φ(φ + 2ir), which means that e 'mi* =
eimiW+2"·) o r e >2Tml _ I This requires that m i be a positive or negative integer; that is,
mi = 0, ± 1 , ± 2 , . . . , as indicated previously in Section 3.4. T o determine C, we apply
the normalization condition, which in this case becomes Jj; *Φ*Φ άφ= I or

J J (C *e~ imi*) (CeimI*) άφ = \C\*fQ ' άφ = 2x|C|2 = I,

or, assuming C is real, C = \/s/'2ir. Therefore the normalized proper functions of the
2 -component of the angular momentum are

Φ (φ ) = - i = Cim"*, m, = 0, ± 1 , ± 2 , . . . , (3.22)
V z TT

and the proper values L 1 = mjft are integral multiples of ft.

The square of the magnitude of the angular momentum is given by the operator
L2 = Li L2 + L?, where L2 and Ly are operators similar to L., as given by Eq. (3.20).
Transforming to spherical coordinates, by means of an elaborate algebraic manipulation,
shows that the square of the angular momentum is represented by the quantum operator

i d ( . „ . i
L2 = - t f i — I sin Θ — 1-1— :----- —— (3.23)
sin 0 dO V 50J sin2 Θ θψ-’ J

The proper equation is L2Ttfl1(A) = L 2YiO. φ), where the proper function, which depends
on the angles fl and φ, has been designated by Υ (θ.φ ) and the proper value is L 2. This
corresponds to the differential equation

I d ( . a dY\ , I d2Y , IJ2 .

sin fl dfl \Sm 00 J 1 sin2 fl 9φ2 ' A2

It can be shown that to obtain a solution satisfying the requirements of quantum

mechanics, it is necessary that L 2/A2 = 1(1 + I), where / is a positive integer; that is,
I = 0, I, 2, 3, . . . In this form we have obtained the results previously stated in
130 Atoms with one electron (3.5

Section 3.5; that is, I.2 = 1(1- f I )A2. The solutions of the resulting equation,

i β ( dE\ I 521
^ + 1 ( 1 + I) Y = 0 ,
sin Θ 00 \S,n 90 ) sin2 0 9Θ2

are designated by E im, and are the functions given in Table 3-4. The table shows that
the functions Y imi are the products of one factor depending on 0 and another depending
on φ. [The φ-faetor is identical to Eq. 3.22.] That is, E im, = I'™' (cos 0) Con­
sidering that the l ' i m( are proper functions of the operators L2 and L11 we may then write

L2E im, = 1(1- D h2Y Im 11 L--Eim, = WiiA E im

E X A M P L E 3.5. Analysis of Schrodinger’s equation for motion under central forces.

S o l u tio n : W e recall from Eq. (2.9) that Schrodinger’s equation for motion with a
potential energy E p(r) is

Φ - f E p(r)ip = Εφ.
2 »i \9a· 2 9y2 ' Oz1)

If we now change from the rectangular coordinates x, y, z to the spherical coordinates

r, 0, φ, this equation, after a lengthy algebraic manipulation, becomes

_ A 2 d2 2 <1 + 1 I o_( . . a V _ j_ ϋ '

2m Idr2 r Or r2 .sin O d O y m a o ) sin2 0 θφ2

Ε„(τ)Φ = Εφ.
Recalling Kq. (3.23) for the operator L2, we may write

- 2m (fi
\9r2 +~ f _ sn)
r dr h2r 2J + φ Ε ρ {τ )φ =
Ε φ ·

If we set φ = R (r)Y im t(0,Φ) and recognize that L2E im, = 1(1-f IJA2E im,, the above
equation becomes

_ A2 T d 2 2 d 1(1+ D
R + E p(r )R = E R .
2m \_dr2 r dr

This is an equation that contains only the radial part R(r) of the wave function φ. I t is
customary to set R(r) = n(r)/r, resulting in

A2 rf2* ^ „ , 1(1+ DA 2
J u = Eu. (3.24)
2m dr2 p 2mr

This is sometimes called the radial Schrodinger equation. Comparing this equation with
the one-dimensional Schrodinger equation (2.3), we conclude that the radial motion is
equivalent to a one-dimensional motion under an effective potential energy given by
Eq. (3.19); that is,
 I

3.5) One-eleclroii ware fun d ions under central forces 131

The term K pst„ = 1(1 -T \)h2/2mr2 is a centrifugal potential because the corresponding
“ force,” F = —dEp,„.n/dr is positive and hence is directed away from the origin.
When we set Ep(r) = - Z c 2/-Wenr. we obtain a differential equation that admits as
solutions, for motion under coulomb forces, the radial functions given in Table 3-6. For
other forms of the potential energy, different radial functions result.

E X A M P L E 3.6. Helativistic correction of the energy in hydrogenlike atoms.

S o lu tio n : As we explained in Section 2.12, Schrodinger’s equation (3.3) is obtained by

means of the nonrelativistic expression E — p2/2m„ - f E p. This procedure is correct
whenever the velocity of the electron is very small compared with the velocity of light.
The value of v/c for an electron in a stationary state was estimated in ENampIe 3.1 and
found to be of the order of 7 X 10~ 3Z/n. The relativistic effect due to this velocity,
although very small, can easily be detected by spectroscopic methods. The relativistic
energy of an electron moving with momentum p and having a potential energy E p (see
Eq. A .11) is

E = r\/ m'~c- + p - + E p — mec2,

where the rest mass energy has been subtracted so that the zero of energy coincides with
the nonrelativistic case. Assuming that the momentum p is much smaller than mcc, we
may expand the radical up to the second-order term, resulting in

V “ O ^ 2 - - V i ?4+ · · · + Ep
Smtc

=U
V- r p2 + K) / - rSmcC
^ ] , i + ··· (3-25)

The two terms inside the parentheses give the nonrelativistic approximation for the
energy. Therefore the last term is the first-order relativistic correction to the total energy
of the electron, which we shall designate by A E r. Thus

AEr = 1- p - 1_ ( V \ ( V \
Snitc- 2" ^ 2 \ W \ W

The identical terms inside the parentheses correspond to the nonrelativistic kinetic
energy of the electron. So (as a reasonable approximation) we may write for the first one,
using the result of Eqs. (3.10) and (3.13),

V.
2 mc
I mjl2 = _
' 4 ? re o (2 r) T i r io r
= Ze2
4 7 rto (2 r)
=
_/?.

For the second, we may write p 2/2mc = %mL.v2. Therefore

XEr = - ( - E H h m r 2) = I E.
I /IieC 2 4 c2

Ihus the relativistic correction is of the order of (r/ c)2 times the energy of the electron.
In the hydrogen atom, for example, (v/c)2 is of the order of IO- T and therefore A E r ~
IO- j E, or about 0.001% of E , a quantity which, although small, can easily be detected
in the laboratory with experimental techniques now in use.
132 Atoms with one electron (3.6

T o obtain a more precise result, we note that the last term in Eq. (3.25), which we have
just seen is very small compared with the first two, may be considered as a small pertur­
bation. T o compute its effect on the stationary states, we may estimate its average or
expectation value, according to Eq. (2.50). Therefore in the state described by the wave
function Ipniml we have

AEr = - - \ - 2 (p4)„v, TTTy Iptlm, P 4 Pnlml IlT.

X m vC Smic2 J

The result of this calculation is

1τ ι ) ·
where
a — C2ZATTeJic ~ 1/137

is called the fine structure constant and |A'„| is the absolute value of the energy as given by
Eq. (3.5). The energy levels, in our approximation, are thus given by E — E n + AE,.
Since the relativistic correction (3.26) depends on I as well as on n, levels having the same
n but different I do not have the same energy. In other words, the relativistic correction
destroys the accidental degeneracy we found in the case of a coulomb field. Also the
relativistic correction is always negative for all n and I. For a given n, the smaller the value
of I, the larger the relativistic correction. Thus the states for which the correction is most
important in hydrogen are Is and 2s.
A more refined relativistic theory of the electron has been developed by I’ . A. M . Dirac.
In Dirac’s theory, from the outset, a Schrodinger equation corresponding to the relativistic
energy is set up, and in this way the exact energy levels are obtained. However, his
theory is too complicated to be presented here.

3 .6 T h v Zvvntan K fivvt
Space quantization m anifests itself in a strikin g w ay when the electronic m otion is
disturbed b y an applied m agnetic field. U m ler a sufficiently strong m agnetic field,
each spectral line in a one-electron atom becomes a triplet, consisting o f three
closely spaced lines. T h e spacing is the same for a ll atom s and lines and is pro­
portional to the m agnitude o f th e m agnetic field. T liis effect was observed for the
first tim e in 1896 b y the Dutch physicist P ie te r Zeeman (1865-1943). I t has been
named the Zeeman effect, to honor his work.
A n electron describing a circular o rb it with an angular v e lo c ity ω passes each
point in the orbit ω/'2π tim es per second and therefore corresponds to a current
I = β (ω / 2 π ). Since the current loop is v e r y small, it is equ ivalent to a m agnetic
dipole whose m agnetic m om ent is equal to current tim es area. T h erefore, the
orbital magnetic dipole moment o f the electron is

M l — β (ω / 2 π )(π Γ 2) = ^ecor2.

R eca llin g th at for a circular o rb it L = m^vr = mcwr2, we h ave M l = (e/2m c) L .

T h is is a relation between the m agnitudes o f M l and I.. N o w the direction o f L is
related to the direction o f m otion o f the electron, as shown in F ig . 3-15. On the
other hand, the charge o f the electron is negative, and th erefore the equivalent
3.6) The Zeeman effect 133

F ig . 3-13. Relation between the orbital F ig . 3-16. Precession of the angular mo-
magnetic moment and the angular momen- mentum under the action of a magnetic
turn of an electron. field.

current is opposite to th at o f the electron m otion, resulting in an orientation o f M l

which is opposite to th at o f L . T h u s w e m ay w rite the ve cto r equation

(3.27)

Although w e have obtained this relation for a circular orbit and have used classical
mechanics, this expression still holds true in quantum mechanics for an arb itrary
motion w ith angular m om entum L . T h e Z-com ponent o f the orbital m agnetic
m om ent is

M lz = ~ ο ^ Γ - μ α,η ι, (3.28)
M ffl'Q

where the q u a n tity

μα = = 9.2732 X IO-24 J T -1 = 5.6564 X IO -5 e V T -1

2 TO
c
(3.29)

is called a B ohr magneton.

W hen a m agnetic dipole o f m om ent M is placed in a m agnetic field <B, it acquires
an energy E « = — M · <B. T herefore, when an atom is placed in a m agnetic field,
the additional energy o f an orb itin g electron due to the external m agnetic field is

E iB = -M l ■« = L · «. (3.30)
“ Wc

A t the same tim e, the electron experiences a torque

T = M l x (B = — L x (B,
2 ?ne

which makes the angular m om entum L process around the direction o f the m agnetic
field <R, as indicated in F ig. 3-16. T a k in g the Z-axis parallel to the m agnetic field (B,
13b Atoms with one electron (3.6

-+ 2
.+ I -+ I
- O - 0
--I --I

+1
-0 0
-I 0 + 1 -I
Ami mi V V V
(a) -I 0 +1
Ami mi

(b)

Fig. 3-17. Splitting of s-, p-, and d-energv levels under the action of a magnetic field.
The separation of successive levels is μ »® .

w e can rew rite Ecp (3.30) as £ ® = — M u ® or, using E q. (3.28), w e have

EiB = Pb © «I+ (3.31)

W e then see that E®, instead o f having a continuous range o f values, m ay have
'21 + I distinct values corresponding to eacli o f the '21 + I possible orientations o f
L relative to ® , all equally spaced by the am ount mb®.
T h e total energy o f an electron bound to an atom placed in m agnetic field is
E n + E®, where E n is the energy o f the electron’s m otion in the absence o f a
m agnetic field. T h e refo re E q. (3.31) indicates th at each energy level w ith quantum
numbers n I splits in to 21 + I levels in the presence o f a m agnetic field. T h e
separation between successive levels is also reflected in the frequencies associated
w ith the transitions between the levels. T lie situation fo r s-, p-, and d-levels is
illustrated in F ig. 3-17. States with I — 0 (o r s-states) are n ot affected b y the
m agnetic field. States w ith I = I (o r p-statcs) are split into three equally spaced
states, corresponding to orientations in which m i = + 1 , 0, and — I. Thus the
transition p —> s becomes a triple transition, one corresponding to m i = 0 —>
m i = 0, w ith the original frequency, and tw o others corresponding to m i =
± 1 —» m i — 0 , w ith a frequency difference given by

Au = ± = 1.40 X lO 10® H z. (3.32)

Ii

So each o f the single lines p —* s shown in F ig. 3-8 becomes three closely spaced
lines. Sim ilarly, states w ith I = '2 (o r d-states) are split into five equally spaced
3.7) Electron spin 135

levels corresponding to the orientations o f L given b y m i = ± 2 , ± 1 , 0. The

transition d —> p now has nine possibilities, according to the selection rule A m i =
± 1 , 0. H ow ever, transitions corresponding to the same value o f A m i all have
the same energy change and therefore y ield the same spectral line. W e then
conclude th at although there are nine possible transitions, the spectrum o f the
d —> p transition under a m agnetic field contains on ly three lines, w ith Av still
given b y E q. (3.32).
T h e quantization o f angular m om entum clearly explains the experim ental facts o f
the Zeeman effect. I f instead o f space quantization, the angular m om entum could
have an y orientation, the effect o f the m agnetic field would be to broaden each level.
T h e new levels would then occupy an energy band o f w idth 2pn<RL and each line
would become a band. T h is is w h y, as w e m entioned before, the Zeeman effect is a
proof o f space quantization. In fact, the Zeeman effect was one o f the phenomena
th at prom pted introducing the idea o f the quantization o f angular momentum.
‘V·

3 .7 K levtron Spin

L e t us recall th at the earth, in addition to its orbital m otion around the sun, has a
rotational or spinning m otion abou t its axis. T h erefo re the total angular m om en­
tum o f the earth is the ve cto r sum o f its orbital angular m om entum and its spin
angular m om entum . B y an alogy we m ay suspect that a bound electron in an atom
is also spinning. H ow ever, w e cannot describe the electron as a spherical spinning
particle because o f our ignorance o f its internal structure. Thus w e cannot com pute
the spin angular m om entum o f the electron in the same w ay th at we com pute the
spin angular mom entum o f the earth in terms o f its radius and angular v elocity.
T h e idea o f electron spin was first proposed in 1926 b y G. Uhlenbcck and S. G oud-
sm it to explain certain features o f the spectra o f one-electron atom s (w e shall
consider these in Section 3.9). I f S is the spin angular m om entum o f an electron
and L is the orbital angular mom entum , the total angular m om entum is J = L - f S.
F or given values o f L and S, the value o f J depends on their relative orientation, and
we m ay expect this to be reflected in certain atom ic properties; this indeed is the
case.
T h e existence o f electron spin is borne ou t b y a large accum ulation o f experi­
m ental evidence. F o r example, electron spin is manifested in a v e ry direct w ay by
the Stern-Gerlach experim ent, first perform ed in 1924. Because the electron is a
charged particle, electron spin should result in an intrinsic or spin m agnetic dipole
m om ent M s o f the electron. I f the electron could be described as a rotatin g rigid
charged body, the relation between M s and S would be the same as between M /,
and L , as given by E q. (3.17). H ow ever, this is not so, and w e must w rite

where <js is called the (jyromagnetic ratio o f the electron. T h e experim ental value
for g s is 2.0024. F o r most practical purposes, w e can make gs = 2. T h e total
136 Atoms with one electron (3.7

m agnet ic d ipole m om ent o f an orb itin g and spinning electron is therefore

M = M l + M s = - 2^ ( L + gs S ), (3.33)

and, o f course, depends not on ly on the m agnitudes o f L and S but also on their
rela tive orientation.
Suppose now th at a beam o f hydrogenlike atom s is passed through an inhomo-
geneous m agnetic field, as shown in F ig. 3-18. T h e effect o f such a m agnetic field
on a m agnetic dipole is to exert a force whose direction and m agnitude depend on
the rela tive orientation o f the m agnetic field and the m agnetic dipole. F o r example,
i f the m agnetic dipole is oriented parallel to the m agnetic field, it tends to m ove in
the direction in which the m agnetic field increases, while if the m agnetic d ipole is
oriented antiparallel to the m agnetic field, it w ill m ove in the direction in which the
m agnetic field decreases.
Spin up

In the Stern-Gerlach experim ent the inhomogeneous m agnetic field is produced

b y shaping the pole faces as shown in Fig. 3-18. T h e m agnetic field increases in
strength in the S - N direction. I f the hydrogenlike atom s are in their ground state,
the orbital angular mom entum o f the electron is zero (s-state or I = 0) and the
entire m agnetic m om ent is due to the spin. T h e refo re the atom ic beam will be
d eviated b y the m agnetic field, depending on the orientation o f M s , or, which is
equivalent, the orientation o f S. T h e result o f the experim ent is th at the atom ic
beam is split in tw o b y the inhomogeneous m agnetic field. T h is shows that

the electron spin may have only two orientations relative to the magnetic
field : either parallel or anliparallel.

Since, according to our discussion in Section 3.4, the number o f orientations o f an

angular mom entum vector rela tive to a fixed Z -axis is g = 21 + I , fo r the case o f
spin we have the value g = 2 or I = £. D esign ating the spin quantum number by
s instead o f I and the quantum number corresponding to the com ponent S z by m „
3.8) Addition of angular momenta 137

we then have that s = % and m , = ±J. Then X

S2= s(s + I )h 2 = Jft2, s = i,

S j - m ,h, τη, = ±£.

T h e on ly tw o perm itted values o f m , (th a t is, and — i ) ,

corresponding to the tw o possible orientations o f S, are
shown in Fig. 3-19. F o r b re v ity they are usually referred
to as spin up ( | ) and spin down ( I ) , although the spin is
n evertactu ally directed along the Z-axis or opposite to it.

F ig. 3-19. Possible orientations of the spin relative to the Z-n\.. .

W e shall designate th e w a v e function associated w ith the S j -Coniponent o f the

spin b y Xm,. T h e exact form o f Xm, is o f no concern to us; its main properties are
that
S2Xm. = J fl2Xm1, Sj Xm. = JWj IiXm,.

Som etim es w e use, instead o f Xm,, the notation x + and x _ , corresponding respec­
tiv e ly to m , = + 5 and — £. T h e n the com plete w a ve function o f an electron
m ovin g in a central field is

y
Pnlmimi ~ I lmiid, (3.35)

N o te from E q . (3.35) that, to com p letely describe the state o f an electron in a

central field, fo u r quantum numbers are required: n, I, mi, and m ,.
T h e properties o f the electron spin, described by E q. (3.34), cannot be explained
in terms o f any classical m odel o f the electron. H ow ever, w e can explain them
th eoretically when w e com bine the ideas o f quantum mechanics w ith the principle
o f rela tivity. T h is was done b y D irac around 1928, but w e shall not discuss
his analysis here, since it is beyond the scope o f this book.
W h en the atom is in a state in w hich I Ti 0 , the sp litting produced b y the m ag­
netic field depends on th e total m agnetic m om ent, o r— which is the same thing—
on the total angular m om entum J = L + S. T h erefore the Stern-Gerlach experi­
ment can be used to determ ine the total angular m om entum o f the state o f an atom.

It.ft A d d ition o f A n fftda r Altnnrntfi

In the previous section w e saw th at the resultant angular m om entum ./ o f an
electron in a hydrogen like atom is the sum o f the orbital angular m om entum L and
the spin angular m om entum S ; th at is, J = L + S. I t is im portan t to exam ine the
possible values o f J according to quantum mechanics. So th at our analysis m ay be
generally applicable, let us suppose that, w e have tw o angular m om enta, designated
by J I and J 2, which m ay, fo r exam ple, correspond to the orbital angular m om entum
138 Atoms with one electron (3.8

o f an electron and its spin (as w e have just considered in the preceding section), or
the angular m om entum o f tw o electrons in an atom (a case which w e shall consider
in the next chapter). T h en J\ = j i ( j i + 1 )^2>J u = » « i K and J\ = J 2 U 2 + 1 )^ 2>
J 2z = m 2h. I t can be shown that in the m ost general case J 1 and J2 can be either
integers or h a lf integers; that is, 0, I, f , 2 , . . . A s explained before, orbital
angular m om enta can on ly be integers.
U J = J x A - J i >s the resultant angular m om entum , so th at J z - J \z + J 2z,

then
J 2 = JU + 1)Λ 2, Jz = mh, m = ± j, ± U - I), · · · (3.36)

w ith w == Ot1 + Ot2. B u t because J i and J 2 m ay have different rela tive orienta­
tions, there are several possible values o f J. Thus w e find th at the quantum num­
ber,/ varies in unit-sized steps from J 1 + J2 dow n to IJ1 — J2|, so th at it can attain
on ly the values

J = Ji + 32, Ji + 32 — I, J i + 32 — 2, . . . , IJi — J2|.

T h e first valu e corresponds to J i and J 2 “p a ra lle l” and the last value to the tw o
angular m om enta “a n tip ara llel.” Successive values o f J d iffer by one unit, and if
J 2 < J o the total number o f possibilities is

/.

Fig. 3-20. Possiblerelativeorientations

of L and S, when I = 2.

j = l+ k (spin up)
( a) (b)

F o r exam ple, if J2 = £, the possible values o f J are J 1 + £ and J 1 — J, cor­

responding to parallel and antiparallel orientations. Thus, in the case o f an electron,
i f J i = L and J 2 = S, w e h ave th at the possible values o f the total angular
m om entum J are j = I dt T h ese tw o situations are illustrated in F ig. 3-20 for
I = 2. H ence w e have that

the electron spin may have only two possible orientations relative to the
orbital angular momentum.

W hen Z = 0 (o r s-state) on ly j = h is possible. W h en w e indicate the value o f J

as a subscript, the possible states o f an electron in a central field are designated as
shown in T a b le 3-7.
3.9) Spin-orbit interaction 139

T A B L E 3-7 Designation o f Electronic States

I 0 I 2 3

i i 4 I § I 4 i

Symbol Sl/2 Pl/2 P 3/2 d3/2 ds/2 fs/2 f7/2

A s another illustration, if J2 = I and j ] > I, then j = j j + I , j , or J i — I. It

m ay be sjiotvn th at in an electric dipole transition the photon carries an angular
m om entum corresponding to a j-v a lu e o f I. T h en if J 1 refers to the orbital angular
m om entum I o f the electron and J 2 = I to th at o f the photon, the allowed values
o f the orbital angular m om entum o f an electron a fte r em ittin g or absorbing the
photon are I + I, I, and I — I , corresponding to A l = ± 1 , 0. A s w e explained
previou sly in Section 3.4, Δ/ = 0 is ruled out by p arity considerations.

il.ff S p in -O rb ii In irra rtio n

T h e double orientation o f the electron spin rela tive to the orbital angular m om en­
tum g ives rise to an im portant effect: the doubling o f energy levels (except s-levels)
o f hydrogenlike atoms. T h is doubling o f levels in turn g ives rise to a doubling o f
the spectral lines. T hese lines appear in pairs, having frequencies or wavelengths
which arc v e ry close and are therefore called doublets. T h e best-known doublet is
that composed o f the tw o y ello w or D-Iines o f sodium, corresponding to w avelengths
o f 5890 A and 5896 A . I n fact, it was the problem o f explaining these doublets
which first g a v e rise to the idea o f an electron spin w ith tw o possible orientations.
T h e doubling o f the energy levels is a consequence o f the so-called spin-orbit
interaction. T h e origin o f this interaction is as follow s: in a fram e o f reference X Y Z
attached to the nucleus o f an atom , the electron appears to rev o lve around the
nucleus (F ig . 3-21a) w ith angular m om entum L . B ut, in a fram e o f reference
X ' Y ' Z ' attached to the electron it is the nucleus which appears to re v o lv e around

Z Z'

(a) 0>)

Fig. 3-21. Origin of the spin-orbit interaction.

 Atoms with one electron 13.9

th e electron. T h e nucleus, since it has a p ositive charge, produces a m agnetic field

(Ά in the X ' Y ' Z ' fram e which is parallel to the angular m om entum L . Since the
electron is a t rest rela tive to X 'Y 'Z ', the on ly interaction o f the nuclear m agnetic
field is w ith the elcctron-spin m agnetic m om ent M s - T h is interection is propor­
tional to M s ■ ® . B u t <B is parallel to L and M s is parallel to S. T h e refo re the
interaction is proportion al to S · L . T h is is w h y this effect is called spin-orbit
interaction. VVe m ay then w rite, for the energy o f the electron due to the spin-
orb it interaction,

E sl — aS · L , (3.37)

w here a is a qu a n tity which depends on the d ifferent variables affectin g the

electron’s m otion and whose precise form w e need not know a t this tim e. G iven
th at E n is the energy o f the electronic m otion, assuming o n ly a centra! force, then
the total energy, when the spin-orbit interaction is added, is

E = En + E sl = E n + aS · L . (3.38)

W h en we w rite this expression w e assume that the spin-orbit interaction does not
affect the contribution to the energy due to the central forces, a va lid assumption
so long as E sl is v e ry small com pared w ith E n. F o r a given value o f L and S, the
spin-orbit interaction E sl depends on the rela tive orientation o f these tw o vectors.
B u t since S can have on ly tw o possible orientations rela tive to L , we conclude th at

the spin-orbit interaction splits each electron energy level with a given
value o f I into two closely spaced levels.

One level corresponds to L and S parallel or spin up ( j — I + i)> anc^ t f'c other to L
and S antiparallel or spin down ( j — I — 2)· O bviou sly s-lcvels (I = 0) remain
single.
In the presence o f a spin-orbit interaction the quantum numbers needed to
specify the angular m om entum state o f an electron are I, j , and m, where m refers
to the proper value o f J 2. T h e selection rules fo r electric-dipole transitions re­
quired b y the conservation o f angular m om entum are

Al = ± 1 , A j — 0, i I, Atn — 0, ± 1 . (3.39)

T h e transitions w ith A j = 0 are v e ry w eak because they require a reversal o f the

direction o f the spin rela tive to the orbital angular m om entum o f the electron.
B u t the force th at would produce such spin reversal is the spin-orbit interaction,
which is a rela tiv ely w eak force.
F igu re 3-22 depicts (n o t to scale) how the levels shown in Fig. 3-7 are affected
by the spin-orbit interaction, and some o f the possible transitions. T h e rela tively
weak transition d 3/2 —> p3/2 is indicated b y a dashed line. W e see th at spectral
lines corresponding to transitions between s- and p-levels are therefore doublets,
while those between d- and p-lcvcls arc triplets, although one of the lines is so weak
th at one m ay speak o f a doublet.
3.9) Spin-orbit interaction 141

I= O I= I 1= 2

Fig. 3-22. Spin-orbit splitting of energy

levels and possible transitions. The dashed
line indicates a transition with very low
probability:

E X A M P L E 3.7. Calculation of the separation of two energy levels due to the spin-orbit
interaction.

S o lu tio n : Our purpose is to compute the value of E si. for the two cases of spin up and
spin down, and find their difference. This difference gives the splitting of the energy
levels. T o do this, we must find S - L in both cases. Now J = I. + S and therefore
J 2 = L 2 -J- S2 -J- 2S · L , from which we obtain

S -L = a J2 - L2 - S2).

Inserting the values of L 2, S 2, and J 2, as given by Eqs. (3.15), (3.34), and (3.36), we
obtain
S - L = i O O + 1) - f ( f + D - f ’ A2
or
(£M2, spin up, j = I + £,
S -L =
I - \ (l + 1)Λ2, spin down, j = I — (L

Thus, when we use Eq. (3.38), the energy levels become

E( T ) = E n -f- E s l ( T ) = E n + ia lh 2, j - l + i,
E( I ) = E n + Esd I ) = E n - ia (l + I )k 2, j = I - £.

Thus, if ais positive, levels with j = / + £ are slightly raisedand those with j = I — h
are slightly lowered relative to the central force energy level E n. T o complete our calcula­
tion we must evaluate a, but since this calculation is beyond the level of this book, we
shall limit ourselves to producing the final result, which is

\En\Z*a2
a W nW +DV + i ) ’

where a is the fine structure constant, introduced in Example 3.6, and \E„\ is the absolute
value of the energy of the electron in the absence of spin-orbit interaction.
The separation between the two energy levels is

\En\Z2a 2 ,-s \En\Z2

^ E s l = \ah2( 2 l + I ) = 5.32 X 10
n l ( l + I) n l(l + 1)
142 Atoms with one electron (3.9

Thus the separation between the levels due to the spin-orbit interaction is very small
compared with |i?„|, and decreases as n and I increase. For example, for the 2p-state in
hydrogen, A E s l is about 4.6 X IO-5 eV. So the transition from the 2p-state to the Is-
state should consist of two lines separated in frequency by an amount 1.11 X IO10 Hz or a
wavelength difference of about 5.3 X IO-13 m. These values should be compared with the
frequency 2.47 X IO15 Hz and the wavelength 1.21 X IO-7 m corresponding to the
transition in the absence of the spin-orbit interaction.

1 States

2 ds/2
1, 2 P3/2, dj/a
n = 3-

•0 , I S | / 2, p I /2

I States
I P3/2
•I l>3/2

0.365 cm-1

» = 24
0.035 cm-1
I ... 0 S |/2
K 1 Pl/2
o, I S |/2 , P l/ 2

F ig. 3-23. Fine structure of the n = 3 —* n = 2 Fig. 3-24. Splitting of the n = 2 level
transition in hydrogen. in hydrogen, including the Lamb shift.

When the relativistic correction given by Eq. (3.26) is added to the spin-orbit inter­
action, the energy levels are given, up to the first-order approximation, by the expression

and thus levels with the same n and j coincide. Level n = I has,/ = 5 only and remains
single. Energy levels for n = 2 and n = 3 and the allowed transitions among these levels
are shown in Fig. 3-23 for hydrogen. More careful measurements and more precise
calculations show that states with different I but the same j do not coincide, but in fact
are slightly separated. For example, the actual level arrangement for 71 = 2 is as shown in
Fig. 3-24 for hydrogen. The separation between the S 1/2 and the p i/2 levels is called the
Lamb shift.

E X A M P L E 3.8. Calculation of the magnetic moment of an electron in the presence of

spin-orbit interaction.
3.9) Spin-orbit interaction 143

S o lu tio n : The spin-orbit interaction E Sl — aS · L depends on the relative orienta­

tion of S and L\ that is, on the angle formed by these two angular momenta. But when the
potential energy depends on an angle, a torque is applied in a direction perpendicular to
the angle. Thus a torque exists perpendicular to S and L which makes these vectors
precess. However, if no external torques are applied, the total angular momentum
J = L + S must be constant. So we may visualize the effect of the spin-orbit interaction
as producing a precession of S and L around their resultant, as indicated in Fig. 3-25.

Fig. 3-23. Resultant average magnetic

moment.

The magnetic dipole moment of the electron, with gs ~ 2, is given in Eq. (3.331 by

M = — (e/2m ,)(L + 2 S ) ------ (e/2mc) ( J + S)

and is not directly opposed to J. Therefore M is also precessing around J. The average
value of M is equal to the component of M parallel to J. So we may write

Mave = { M · UJ)UJ,
where u ; is the unit vector in the direction of J, which may be written as u j = J/J.
Therefore
Mave = - (e / 2 me)U + S) · J J/ J2 ------ (e/2me) ( l + S · J/ J2)J.

Since J = L + S, we may write S - J = £ (J 2 + S2 — L 2). Thus, when we replace the

squares of the angular momenta by their quantal expressions, we finally have

Mave — (e/2me)gj,
where
j Q + ! ) + « ( « + 1) ~ K l + l )
(3.40)
2) 0 · + I)

is called the Lande factor. Its values for spin up and spin down are

(3.41)

In the presence of a weak magnetic field which does not appreciably disturb the dynam­
ical relations of Fig. 3-25, the interaction energy is

Em = -M a v e · CB = (e/2mc)g<RJz = MBffCBm. (3.42)

This results in more complicated Zeeman patterns than those considered in Section 3.6.
The Zeeman effect, as given by Eq. (3.42), is very important because it allows us to find g
experimentally and from it verify the values of j and I for the electron’s state. The results
of Section 3.6 are still valid when the magnetic field is strong, so that the magnetic inter­
action is much larger than the spin-orbit interaction and the latter can be ignored.
 Atoms with one electron

Kvfprt>nees

1. “ Papers Given at the Niels Bohr Memorial Session,” A. Bohr, F. Bloch, J. Neilson,
J. Rosenfcld, V. Weisskopf, and J. Wheeler, Physics Today, October 1963, page 22
2. “ The Evolution of the Balmer Series,” L. Banet, Am . J. Phys. 34, 496 (1966)
3. “ Orbital Angular Momentum in Quantum Mechanics,” M. Whippman, Am. J. Phys.
34, 656 (1966)
4. “ A Quantum-Dynamical Description of Atoms and Radiative Processes,” G. Fowles,
Am. J. Phys. 31, 407 (1963)
5. Elements of Wave Mechanics, N . M ott. Cambridge: Cambridge University Press,
1962, Chapter 4, Sections 4-13; Chapter 5, Sections 1.2.1 and 4.3
6. Principles of Modern Physics, R. Leighton. New Y ork : M cGraw-Hill, 1959, Chapters
5 and 6
7. Atomic Spectra and Atomic Structure, G. Herzberg. N ew Y o r k : Dover, 1951, Chapter I
8. The Behavior of Electrons in Atoms, R. Hochstrasser. New Y ork: Benjamin, 1964
9. Structure of Mailer, W. Finkelnburg. New Y ork: Academic Press, 1964, Chapter 3
10. Quantum Theory of Matter, J. C. Slater. N ew Y ork : M cGraw-Hill, 1951, Chapter 5
11. Introduction to Modern Physics, R. Richtmyer, E. Kennard, and T . Lauritsen. N ew
Y ork : McGraw-Hill, 1955, Chapter 5, Sections 80-83; Chapter 6, Sections 104-108

K m b lr m s

3.1 Calculate the angular velocity and the
potential and kinetic energies of the
electron in a hydrogen atom as a function
of the quantum number n, assuming that
the electron moves in circular orbits (see
Example 3.1). Evaluate the numerical
coefficients. Plot the calculated values as
functions of n to determine their trend as
the total energy of the electron increases.
3.2 Find the recoil energy and recoil
velocity of a hydrogen atom when it suf­
fers a transition from the state n = 4 to
the state n = I, emitting a photon. From
the result, justify the validity of the as­
sumption that we made when we wrote
Eq. (3.14).
3.3 If the average lifetime of an excited
state of hydrogen is of the order of IO-8 s,
estimate how many orbits an electron
makes (a) when it is in the state n = 2 and
(b) when it is in the state n = 15, before it
suffers a transition to state n = I. (c) Com­
pare these numbers with the number of
orbits the earth has made around the sun
in its 2 X IO8 years of existence.
3.4 Five lines in the Balmer series of
hydrogen have the wavelengths 3669.42 A,
3770.06 A, 3835.40 A, 3970.07 A, and
4340.47 A. Plot v against n for the Balmer
series. By inspection, find the value of n
of the upper level for each of the five wave­
lengths given.
3.5 Compute the wavelength difference
between the H a (that is, n = 3 to n = 2)
lines of hydrogen, deuterium, and tritium
which results from the mass difference of
these atoms.
3.6 Which of the lines of the spectrum of
hydrogen fall in the visible region of the
spectrum (between 4000 A and 7000 A).
Which lines of I I e + fall in the same region?
How could you distinguish whether there
was hydrogen mixed in with a helium
sample?

3.7 Show that for a photon we may use
the equivalences I eV = 8065.8 cm-1 and
I cm-1 = 1.2398 X IO-4 eV.
3.8 Suppose that you were repeating the
Franck-Hertz experiment, using atomic
hydrogen as the vapor. What lines in the
hydrogen spectrum would you observe if
the maximum energy of the electrons was
12.5 eV?
3.9 (a) Using the method of Example 3.1,
compute the frequency of the circular
motion of an electron in a hydrogen atom
in the level corresponding to quantum
number n. (b) Compute the frequency of
the radiation emitted in the transition from
state n to state n — I. (c) Show that the
results of (a) and (b) agree when n is very
large.
3.10 W e can compute the angular momen­
tum wave functions 1Τ „ ( 0, φ) by using the
expression F jm = N imP " (cos 0)e'm*, where
4 ir (I
2 1 + 1 (I -
+
m)!
m )!
is the normalization constant and Rfn( I ) is
the associated Legendre function, defined by
Pf(S) = ( - l ) m(l - |2 ) m ' 2 d P , M
dtT
and
are the Legendre polynomials. Compute
F im for I — 0, I, and 2 and compare with
the expressions given in Table 3-4.
3.11 Show that, according to their defini­
tion (see Problem 3.10), the Legendre
polynomials are of degree I and contain
only even or odd powers of I as I is even
or odd.
3.12 B y direct calculation, determine
whether the wave functions appearing in
Table 3-5 are proper functions of the
operators (a) L21 (b) L?.
3.13 Make a polar diagram of |F|m,|2 for
I = I and mi = 0, ± 1 . Repeat for the
Problems Jb5
angular wave functions pf, p j, and p2 and
compare results.
3.14 Referring to the definition of the
associated Legendre functions in Problem
3.10, show that their parity is equal to
( —I )1 [H in t: N ote what happens when
I is replaced by — ξ in the definitions of
R i ( I ) and P f ( |).]
3.15 In spherical coordinates, the parity
operation r —* — r (or x, y, z —* —I, — y,
—z) is expressed by the transformation
r, θ, φ —> r, -K — Θ, ir + φ. Analyze the
behavior of the angular wave functions
given in 'fable 3-4 and confirm the rule
given in the text that the parity of the
F im, functions is ( — 1)'. Repeat for the
wave functions appearing in Table 3-5.
3.16 (a) Show that the angular wave
functions of Table 3-5 may be obtained by
a proper linear combination of the wave
functions in Table 3-4. (b) Express the
wave functions of Table 3-5 in terms of
x, y, z, and r and justify the notation used
for their description.
3.17 Express the operators L1 and Lv in
spherical coordinates. Using these values,
together with Eq. (3.21) for L1, obtain
expression (3.23) for L2.
3.18 W rite the radial equation (3.24) for a
free particle (E p = 0). Show, by direct
substitution into the equation, that the
solutions for I = 0 and I = I satisfying the
requirement that u = 0 for r = 0 are u =
sin At and u = (sin kr)/kr — cos Ar, where
A2 = 2mE/h2. Write the complete free
particle solution φχ„ (r ), including the
angular part, for I = 0 and 1 = 1. Inter­
pret the wave function I = 0 as a combina­
tion of an incoming and an outgoing
spherical wave. [.Vote; I t can be shown
that the general wave function for a free
particle of momentum p = hk and
orbital angular momentum L —
+1(1 + I )h is φ ι„ = j i ( k r ) Y tm(e, φ),
where Ji(Ar) is called the spherical Hessel
function of order I. The student should
consult a mathematical handbook to
investigate the Bessel functions and obtain
146 Atoms with one electron

jo (k r) and ji( k r ), comparing these with the
results obtained in the first part of this
problem.)
3.19 I t can be shown that the wave
function for a free particle moving along
the if-axis with momentum hk may be
expressed as
I
ψ = e
ikt
= Y j t IV 4 ir (2 f + D j d k r ) Y 10(B).
I
W hy are only mj = 0 wave functions
allowed? W hy does the solution contain
many angular momentum functions? Write
the first two terms in the summation in full.
(See the previous problem for the definition
of j I.)
3.20 The radial wave functions for the
hydrogen atom are given by
R nM = N n ie - " ' 2 P1 L f t i 1 (p ),
3.22 From the information given in
Problem 3.20, show that the radial wave
functions for hydrogen behave as p' for
small values of r and that they behave as
Pne-"'2 for large values of r. Therefore
conclude that the larger the value of I, the
less penetrating the orbit.
3.23 Show, by direct substitution, that
R io is a solution of Schrodinger’s radial
equation.
3.24 Verify that the angular momentum
wave functions Y imi(0, φ) given in Table
3-4 are orthogonal and normalized. (The
condition of orthogonality and normaliza­
tion is that
So S0 * Y*mt Y Pml dil = Si p
where dLl = sin Θ d$ άφ and Satl is I if a = b,
and zero otherwise.)
3.25 The volume element in spherical
coordinates (Fig. 3-26) is

dV = dr dS = T2 dr dtt.
where p = 2Zr/nao, the IJt are the associ­
ated Laguerre polynomials, which are de­
The probability of finding an electron
fined as
within that volume element is |ψ|2Γ2 dr dil.
Verify that the probability of finding the
L \(p) = — [L i(P )J , electron within the spherical shell of radii r
dp
and r + dr, regardless of the angular posi­
where tion, is given by |/?„i|2r2 dr. [H in t: Replace
Φ by its expression (3.18) and integrate over
L i ( p ) = e’ — ' [p‘ e~p\ , all angles, using the normalization condi­
dp
tion for Τι™, given in Problem 3.24.)

and N „ i is the normalization constant given

Z
by

v = _ Γ ( » - * - Ο ’Γ 2
[\naoJ 2n[(n 1) I]3 J

W rite all the radial functions for n = 1,2,

and 3, and compare with the expressions
given in Table 3-6.
3.21 Show that the associated Laguerre
polynomials, defined in Problem 3.20, are
of degree t — s. This shows that s < I.
Thus verify the rule that for a given n the
maximum value of ( i s n — I.

3.26 Using the result of the preceding
problem, find (a) the most probable dis­
tance, and (b) the average distance of the
electron from the proton in the ls-state in
hydrogen. Compare with the Rohr radius
of the orbit when n = I.
3.27 (a) Using the volume element given
in Problem 3.25, show that the normaliza­
tion condition of the ψ „ι„, wave functions
requires that $o\Rni\2r 2 dr = I. (b) R e­
ferring tp Fig. 3-13, show that the area
under each curve is equal to one, as
required by the normalization condition.
[H int: Consider each lobe as a triangle.]
3.28 The average value of r in the
hydrogenlike atoms is given by
Compute r»„c for all states with n - 1,2,
and 3. Compare these values with the
corresponding Rohr radii. Using ί"ftvo BS fl<
measure of the size of the orbit, arrange the
nl states according to increasing average
distances from the nucleus.
3.29 The radial wave functions have one
or more nodes, i.e., regions in which the
probability of finding the electron is zero.
Find the value of r at which this happens
for the 2s-wave function in Table 3-6.
3.30 Using Eq. (3.24), show that, regard­
less of the value of the angular momentum,
the radial wave function of a free particle at
large distances from the origin of coordi­
nates is proportional to e iilcrZr1 where
k2 = 2mE/h2. Hence the complete wave
function can be written as / W e iikr/r,
where }(θ ) depends on the angular momen­
tum. Interpret both signs.
3.31 Write the radial and angular integrals
required to compute the matrix elements of
z = r cos Θ between states nlmi and n'l'm'i.
Show that the matrix elements are zero
unless m i = m\.
3.32 Estimate the fractional relativistic
correction A ErfEn for the n = 2 energy
levels in the hydrogen atom.
Problems 147
3.33 Analyze the splitting of p-, d-, and
f-levels of a one-electron atom as a result of
the relativistic effect. [H in t: See Example
3.6.]
3.34 Determine the electric current of the
electron in the first three Rohr orbits
( n = I, 2, 3). Also calculate the magnetic
dipole moment of the electron for each case.
3.35 Draw an energy-level diagram for the
4f- and 3d-states of hydrogen in the pres­
ence of a magnetic field. Show that in the
4f —* 3d transition, the number of spectral
lines is three. I f the magnetic field is 0.5 T ,
would the lines be observable, given that
the resolution of a spectrometer is 10_1 1 m?
3.36 The value of e/me may be obtained
experimentally by observing the Zeeman
effect. Find the value of e/m* if the separa­
tion between two lines in a field of 0.450 T
is 0.629 X IO10Hz. What is the wave­
length separation for the hydrogen line in
the transition n = 2 t o n = l ? Is the
wavelength separation for the H a line
(n = 3 to n = 2) greater than, less than,
or the same?
3.37 The force exerted on a magnetic
dipole of moment M by an inhomogenous
magnetic field (B of gradient d(&fdz is
F — ± M [dR/dz). Given that the gradi­
ent in a certain region is 1.5 X IO2 T m ~ l ,
calculate the force exerted on an electron
due to its spin magnetic dipole moment. If
a hydrogen atom moves I m in a direction
perpendicular to such a field, calculate the
vertical displacement, given that the
velocity of the hydrogen atom is IO5 m s_ I
and the electron spin is either parallel or
antiparallel to the magnetic field.
3.38 A beam of silver atoms with an
average velocity of 7 X IO2 m s -1 passes
through an inhomogenous magnetic field
0.1 m long which has a gradient of 3 X IO2
T m -1 in a direction perpendicular to the
motion of the atoms. Find the maximum
separation of the two beams which emerge
from the field region. Assume that the net
magnetic moment of each atom is I Rohr
magneton.
ihK Atoms with one electron

3.39 What radiofrequency signal will in­ 3.45 For a relativistic particle moving in a
duce electron spin transitions to change region of potential energy E jt, the total
from parallel to antiparallel orientation (or energy is written E = c V n i2c- -F p 2 4- E jt.
vice versa) in a magnetic field of IO-1 T ? This may also be written as (E — E p) 2 =
3.40 Using Eq. (3.39) verify that the moc4 + P2C2. Write the corresponding
numbers given for the spin-orbit splitting Schrodinger equation for the hydrogen
of the energy levels for hydrogen shown in atom by replacing p with its operator
Fig. 3-23 are correct. Calculate the same —i7iV (see Problem 3.44). [Note: This
splitting energies for H e +. equation does not give the correct relativis­
tic energy levels of hydrogen.]
3.41 It was indicated in Example 3.8 that
the spin-orbit interaction causes a preces­ 3.46 It can be shown that the spin-orbit
sion of L and S about their resultant J , interaction is
which is constant. Show that, in this case,
E sl — I c r
L z and S z cannot have well-defined values 2.2 r dr ’
2mec
even though their sum J z is constant.
Consequently, m i and m , are not good where E p is the potential energy due to the
quantum numbers, wbile m is a good electric interaction with the nucleus. Using
number. the result that
3.42 Analyze the splitting of the 3d-level
Z2
in hydrogen due to a magnetic field (a) (r ) avc =
agn3/(i+ * ) ( ! + I )
when the magnetic field is weak and (b)
when it is strong, compared with the spin-
obtain the expression for the spin-orbit
orbit interaction.
splitting, AEsLt given in Example 3.7.
3.43 Discuss the splitting of the lines in
3.47 According to Example 3.6, the
the 3d —» 2p transition in the presence of a
relativistic correction to the energy levels
magnetic field, when the magnetic field is
in a one-electron atom can be obtained by
weak compared with the spin-orbit inter­
computing the average value of
action.
3.44 The relativistic expression for the
energy of a free particle is E 2 = riigc4 +
P 2C2 . Write the corresponding relativistic where E n is given by Halmer’s formula and
Schro<linger equation, by replacing p with E p — - Z e 2JAirttir is the potential energy
its operator —iftV (according to Table 2-4). of the electron. Using the results
This equation is called the Klein-Gordon
equation, (a) Find the solution correspond­
/avc
ing to a free particle moving along the non
.Y-axis, (b) Show that for a free particle and
with zero angular momentum the wave Z2
function is ψ = Ce-ltrJrl where μ = moc/h (r 2 )„vc =
a2n*(l + i )
is 2jr times the reciprocal of the Compton
wavelength of the particle. obtain Eq. (3.26).
 4
ATOMS W ITH MANY
ELECTRONS

JtA Introdaclion
4 .2 The H elium Atom
4.3 The Exclusion P
4.4 Electronic Structure o j Atoms
4 . 5 L -S Coupling
4.6 Atom s with One or Two Valence Electrons
4.7 X -R a y Spectra
150 Atoms with many electrons (0.2

4.1 In trod u ction

AU atom s— except hydrogen and certain ions o f the lig h t elem ents— contain several
electrons. T h erefo re it m ay seem th at the one-electron problem studied in the pre­
vious chapter is o f little practical value. H ow ever, an understanding o f the proper­
ties o f one-electron atom s is v e ry helpful in an alyzin g m any-electron atoms.
T h e first d ifficu lty w ith the m any-electron atom is the im possibility o f describing
the m otion o f each individual electron because, in ad dition to considering the elec­
trical interaction o f each electron w ith the nucleus, w e m ust consider the m utual
interactions am ong the electrons. T h u s the poten tial energy o f the w h ole atom is

E ” ~ S ~ 4 ^or- + S 4 7 rtO
U i ' (4-1)
e le c tro n s p a irs

T h e last sum mation provides a coupling in the m otion o f the electrons, and hence
w e cannot consider each electron as m ovin g independently o f the others. Any
m odification in the m otion o f one electron must, o f necessity, affect the m otion o f
all the other electrons. T h erefo re we cannot speak o f the individual energy o f each
electron but on ly o f the energy o f the w hole atom (o r ion ). F o r the same reason,
w e do not speak o f a w a ve function for each electron, but on ly a w a v e function for
the com plete atom .
T h e problem o f m any electrons cannot be solved e x a c tly ; therefore certain ap­
proxim ations are required. W e shall illustrate these approxim ations b y discussing
the helium atom.

E lectron I

\
\
\
\
E lectron 2
ri\
Fig. 4-1. A heliumlike atom or ion. \
V
\ n
N u cleus

+Ze

4 .2 The H eliu m A to m
O f all the m any-electron atom s, the sim plest are those w ith tw o electrons, such as
the n egative hydrogen ion H - (Z = I ) , the helium atom H e (Z = 2), the singly
ionized lithium atom L i + (Z = 3), and so on. T h e potential energy o f the elec­
trons in this case (F ig . 4 -1 ) is

J? _ I c , (» o ')

p 47Γe0r t 47Γ€0γ2 47Γ60» ν

4.2) The helium atom 151

T h e first tw o terms correspond to the attraction between the nucleus and eacli o f
the electrons and the last term to the repulsion between the tw o electrons. E ven
for this rela tively sim ple problem o f o n ly tw o electrons, it is impossible to solve
Schrodinger’s equation e x a c tly ; it is necessary to m ake several approxim ations.
Since the m athem atical discussion o f helium like atom s is beyond the scope o f this
book, w e shall lim it ourselves to a physical description, follow ed, in E xam ple 4.2,
by a b rief explanation o f how the energy is calculated.
A s a first approxim ation, we m ay ignore the last term (o r the electron-electron
interaction term ) in E q. (4.2). T h is is equivalent to assuming th a t each electron
moves independently o f the other. Thus we m ay call this approxim ation the
independent-particle model. T h erefo re the m otion o f each electron can be described
by hydrogenlike w ave functions o f the ty p e ^nimt = Z?nf(r)Eim,(0, Φ), specified by
the orbital quantum numbers n, I, m i. T h e energy o f the atom is obtained b y add­
ing terms o f the form o f E q. (3.5), th at is, E = — R h c Z 2/n2, one fo r each electron.
Hence in the case o f H e, the energy o f the electronic m otion in the ground state,
n = l ( i f w e set Z — 2 in E q. 3.5) would be E hp = 2 X ( — 54.4 e V ) = — 108.8 eV.
T h e experim ental value, how ever, is E He = — 78.98 eV . T h u s our first-order
approxim ation gives an energy which is too low. T h e reason for this is th at we
neglected the repulsion o f the tw o electrons, which tends to raise the energy o f the
atom.
W e can im prove our approxim ation b y considering the perturbation o f the elec­
tronic m otion caused b y the m utual interaction o f the tw o electrons. A plausible
im provem ent is to consider th at each electron m oves n ot on ly in the central field
o f the nucleus but also in an average central field produced b y the other electron.
Thus the apparent net effect o f each electron on the m otion o f the oth er is to screen
the charge o f the nucleus b y a certain am ount. T h e energy o f the atom in the
ground state m ay then be w ritten as

E = 2 (Z - S )2E h ,

where E u = — 13.6 e V (th e energy for hydrogenlike m otion ) and S is the screening
constant, which for the ground state o f helium must have the value o f 0.32 to agree
w ith the observed value o f E He· T h a t is, the screening effect o f each electron on the
other is equ ivalent to about one-third o f the electronic charge.
A s an aid, le t us label the electrons I and 2. Since in our first approxim ation we
assumed that, the electrons m oved independently, the prob ab ility o f finding elec­
tron I a t a given position and a t the same tim e finding electron 2 a t another given
position is the product o f the p ro b ab ility distribution for each electron, because
the tw o events are uncorrelated; that is, Z3atom = 73( l ) / 3(2 ). T h e refo re w e con­
clude th a t in the independent-particle m odel the w ave function o f the atom should
be the product o f the w a ve functions for each electron.* I f we designate the orbital
quantum numbers »/>«> o f electron I b y a and the quantum numbers o f electron 2

* This is also a straightforward conclusion from Schrodinger’s equation for a system of

independent particles.
152 Atoms with many electrons

b y b, w e must then w rite

^atom = t a W t b i 2), (4.3)

resulting in a p rob a b ility distribution

l*atom|2 = |lAaO¥/.(2)|2 = | ^ ( 1)|2|^6( 2)|2. (4.4)

D ue to the m otion o f the electrons, the avera ge central field th at one electron
produces on the other deviates from the 1/r coulom b field produced b y the nucleus.
T h is ob viou sly requires a slight m odification o f the w a ve functions ^ a( I ) and i/'t( 2),
which are no longer identical to the hydrogen like w a ve functions. T h e change
affects the radial part R „ i but not the angular p art Y imi o f the w a ve function be­
cause the resultant force on each electron is still a central force. U sing appropriate
m athem atical techniques, we can optim ize the electron w ave function, and so ob ­
tain the energy levels o f the atom w ith re la tiv ely good accuracy.
H ow ever, even if the functions appearing in E q. (4.3) are so optim ized, this ex­
pression for the w ave function o f the atom cannot be correct. W a v e function (4.3)
says th at electron I is in state a and electron 2 is in state b. B ut the w ave function

'/'atom = Φα( 2 )ψί>( 1 ) (4.5)

corresponding to electron 2 in state a and electron I in state b, must represent a

state o f the same energy as the w ave function o f E q. (4.3) and should describe the
state o f the atom ju st as well as E q. (4.3). T h e fact th at the w a ve functions given
b y E qs. (4.3) and (4.5) correspond to the same energy is called exchancje degeneracy.
N o w , electrons are identical and indistinguishable, and the m ost we can say is
th at in the atom one electron is in state a and the oth er is in state b. T h is requires
th at the w ave function ψ,Μι,η be such th at |i/'»,OJn|2 (which gives the p ro b ab ility dis­
tribution o f both electrons) be sym m etric w ith respect to the tw o electrons, in such
a w ay th at both electrons p lay the same role. N eith e r the atom ic w a v e function
given b y E q. (4.3) nor the one given b y E q. (4.5) m eets this requirem ent. B u t we
m ay obtain an adequate atom ic w a ve function (incorporatin g the fact th at the
electrons are indistinguishable) b y m aking ap propriate linear com binations o f
Eqs. (4.3) and (4.5), which happen to be the functions

’/'atom — - M l ¥ 6 (2 ) ± M 2 )^ (1 ). (4.6)

T h e student can see th at in both cases the expression |^at0m|2 is sym m etric w ith
respect to both electrons. T h e inform ation contained in the functions g ive n by
Eqs. (4.3), (4.5), and (4.6) is expressed schem atically in F ig. 4-2.

S ta te b O O O
·>

2
State a — o — — o —
I' - <ha( I JiM2) ψ= ψ„(2)ψ/,(|)
4.2) The helium atom 153

W e shall henceforth call the w a v e functions given b y E q . (4.6) orbital wave fu n c­

tions, since th ey describe the spatial or orbital behavior o f the electrons in an atom ,
w ithout an y reference to the spin. T h e tw o orbital functions o f E q. (4.6) are v e ry
different in one respect. T h e orbital w a v e function w ith the plus sign,

* s ( I, 2) = * .(1 W »< 2 ) + f . ( 2 ) * ( l ) , (4.7)

is symmetric in the tw o electrons and remains the same if the electrons are ex­
changed; th at is, ψβ(1, 2) = ψϋ(2, I ) . On the other hand, the orbital w ave func­
tion w ith the minus sign,

Φλ (1, 2) = i a W M '2 ) ~ * « ( 2 ) ^ ( 1 ) , (4.8)

is antisymmetric in the tw o electrons and changes sign if the electrons are exchanged;
that is, i M E 2) = — Ψ λ (2, I ) .
This sym m etry b ehavior is reflected in another im portant p ro p erty : T h e energy
o f the atom associated w ith φ$ cannot be the same as the energy corresponding to
φΛ. W e note th at if electrons I and 2 are v e ry close to each other, the tw o terms
which make up those functions are alm ost identical, and therefore Φa is v e ry small
or zero. T h u s the an tisym m etric w a v e function φ Λ describes a state in which the
electrons are never too close and as a result, on the average, have a repulsion
energy which is rela tively small. On the other hand, the sym m etric w ave function
IPs does not exclude the possibility that the electrons m ay be v e ry close a t certain
times, and hence the average repulsion energy o f the state described by φ$ is larger
than that o f Φα · W e are thus faced w ith the follow in g fact:

H eliu m lik e atoms may be in two different slates, with different energies
and atomic orbital wave functions φ$ and φ,\, corresponding to the same
set o f orbital quantum numbers a and b assigned to the two electrons in
the independent particle model.

In other words, a tw o-electron atom has tw o sets o f stationary states and energy
levels, one described by sym m etric orbital w ave functions and the other b y an ti­
sym m etric orbital w a ve functions. T h is purely quantum -m echanical effect is a
consequence o f the fact that electrons are indistinguishable.
T h e on ly exception to the ab ove statem ent is the case in which the tw o sets o f
orbital quantum numbers o f the electrons are identical; that is, a = b. T hen
Φα = Φα(1)Φ<ι('2) — ΦΛ'2)φα{1 ) = 0. Therefore, when the tw o electrons have the
same set o f orbital quantum numbers, on ly the sym m etric o rb ital state is possible.
So far w e have considered on ly the w ave functions which describe the space dis­
tribution o f electrons. A com p lete description o f the state o f the atom requires
that we take the spin o f electrons into account. E ach electron has a spin o f A
T lie spin o f an electron m ay be oriented either parallel or anti parallel to the spin o f
another electron, g ivin g a total spin o f one (S = I ) or zero (.S’ = 0 ).* Spin states

* Values of the quantum numbers for the total orbital angular momentum, total spin, or
their components are designated by capital letters. The corresponding quantities for
individual electrons are designated by lower-case letters.
IbU Atoms with many electrons

w ith S = O are called singlets because th ey can be obtained in on ly one w ay, as

shown in F ig. 4-3. H ow ever, when S = I , the resultant spin v e cto r m ay have
three orientations in space, corresponding to M s = + 1 , 0, and — I. These states
are diagram m ed in Fig. 4-3. T h erefo re spin states w ith S = I have three spin
w a v e functions and are called triplets.

-----
C /
/ S I or
Si
W I,= + k \ / W ,= in,= + i

III,=
or

AI s = +1 Ms = 0
I___
S = I (triplet)

Fig. 4-3. Spin states for a system of two electrons.

I t can be shown that the to ta l spin w ave function o f the singlet (S = 0) state is
antisymmetric in the tw o electrons, while the three total spin w ave functions o f the
trip let ( S = I ) state are symmetric in the tw o electrons. These spin w a v e functions
m ay be expressed in terms o f the one-electron spin w ave functions X ± introduced
in Section 3.7 according to

X,i = - i = [X + (1)X —(2) - X + (2 )x _ (l)], M s = o,

V 2

X + (l)x + (2 ), M s = +1, (4.9)

4 = [ X + (1 )X _ (2 ) + X+ (2 )X _ (1 )], M s = 0,
v 2
x —( l ) x —( 2), M s = -I.

T h e valu e o f M s = m,\ + m , 2 corresponding to the com ponent S 2 o f the total

spin is g ive n for each w a v e function. T h e factor \/\/2 is for norm alization pur­
poses. N o te th a t the w ave functions correspond to the situations described in
Fig. 4-3. Sum m arizing, w e have

S in glet state (S = 0 ): antisym m etric spin w ave function x A,

T rip le t state ( S = I ) : sym m etric spin w a v e functions.Xs-
4.2) The helium alom 155

W e obtain the total w ave function o f the atom by com bining the orb ital w ave
function, given b y or ψΛ, and the spin w ave function, g ive n b y Xs or Xa
that is,
^totai = (orb ita l w a v e function) X (spin w ave function).

T h e sym m etry o f ^totai ob viou sly depends on the sym m etry o f each o f the tw o
factors, and since there are tw o kinds o f orbital w ave functions and tw o kinds of
spin w ave functions there are four possible com binations am ong them . N o w an
examination o f the energy levels o f the helium atom reveals th at the states described
by sym m etric orb ital w a ve functions are alw ays singlets (S — 0) and thus
correspond to antisym m etric spin w a v e functions X.-t, while the states described
by antisym m etric orb ital w a v e functions ψΑ are alw ays triplets (S — I ) , and thus
correspond to sym m etric spin w a ve functions Xs- Thus it seems th a t the on ly
states th at are allowed in nature are

/sym m etric \ /antisym m etricV

'/'total = I orbital w a v e I X I spin w ave I =
\ function / \function
singlets, (4.10)
or

/antisym m etricN /symmetricX

'/'total = I orb ital w a ve I X I spin w ave I = ^ a X s ,
Vfunction / \function /
triplets. (4.11)

In either case Φΐοΐ,ιΐ is antisym m etric, since it is the product o f a sym m etric and an
antisym m etric factor. T h is is a far-reaching conclusion which m ay be stated in a
general form for an y number o f electrons as follow s:

The lotal wave fu n ctio n o f a system o f electrons must be antisymmetric.

In the next section the im plication o f this statem ent regarding m any-electron
atoms w ill be carefully analyzed. N o w we shall b riefly discuss the w ay it affects
the energy levels o f the helium like atoms.
Figure 4-4 shows the energy levels o f helium when one o f the electrons is alw ays
in the ground state Is (orb ital quantum numbers n = I , I = 0, mi = 0) and the
other electron is in the same state or in an excited state. T h e o rb ital quantum
numbers o f the excited electron are shown a t the top as ns, np, ml, etc. T h e energy
values listed are relative to the ground state. Som e o f the possible transitions are
also shown. A tom s w ith S = 0 constitute parahelium and atom s w ith S = I con­
stitute orthohelium. N o te that no transitions betw een the singlet and trip let states
are indicated. Such transitions are qu ite im probable, since th ey in v o lv e a spin re­
arrangement, which is possible o n ly if strong spin-dependent forces are present.
Thus, in a sense, w e m ay regard orthohelium and parahelium as tw o differen t gases.
T h e proportion o f atom s o f each class is three to one. N o te th a t state n = I exists
156 Atoms with many electrons (4.2

on ly when S = O , because in this state both electrons necessarily have the same
orbital quantum numbers and hence the orb ital w ave function must be sym m etric.
Each state o f the helium atom is designated b y a capital letter S, P 1 D , F , etc.,
corresponding to a total orbital angular m om entum o f the atom (which is the sum
o f the orb ital angular m om entum o f the tw o electrons) equal to 0, I , 2, 3, etc. In
each case illustrated in F ig. 4-4, the total orbital angular m om entum is equal to
th e orb ital angular m om entum o f the excited electron, since the other electron has
zero orbital angular m om entum . A superscript to the le ft gives the value o f 26' + I,
or m u ltip licity , which is I for singlet states and 3 for trip let states.
D ue to the spin-orbit interaction, the trip let states consist o f three closely spaced
levels corresponding to the three possible orientations o f the total spin rela tive to
the to ta l o rb ital angular m om entum . T h is is called a fin e structure, and is not
shown in the figure. S-states obviou sly do not show an y fine structure. In addition
to the states shown in F ig. 4-4, there m ay be m any other station ary states, in
which both electrons are excited. H ow ever, w e shall not discuss them here.
 The helium alom 157

E X A M P L E 4.1. Normalize the wave functions t s and t s given by Eqs. (4.7) and (4.8).

S o lu tio n : Let us designate either t s or t s by t - Then, considering that the integral is

taken over the coordinates of both electrons, we have

J t * t dr = J l [ t * ( l ) t * ( 2 ) ± t * (2 )t b (l)\ [t a (l)t b (2 ) ± ^<,(2)^(1)] d n dr2

= J taWtad) άτχ j t*(2)tb(2) (It2

+ J ^ b W t b ( I ) dr I J ^ t* (2 )ta (2 ) Clr2

± J t * ( D t b ( l ) d n j t t t (2 )t a (2 ) d r2

±J t * ( l ) t a ( D dri f t * (2 )t b (2 ) ά τ2.

However, since the proper functions t * and tb are orthogonal (remember Eq. (2.41)), we
have that
J t * ( i ) t b ( i ) d n = J t b ( i ) t a ( i ) d n = 0, i = 1, 2.

Also, the jiroper functions are normalized, that is,

J " t * t i ) t a ( i ) d n = J ^ t l ( i ) t b ( i ) d n = 1, i = 1, 2.

Hence we find that f t * t dr = 2. This shows that t s and t s are not normalized. T o
normalize the wave functions, it is enough to multiply them by the factor 1/ V 2, giving

t s ( I, 2) = -J z \ta(\)tb(2) + t a (2 )t b (l)], M l , 2) = 4 = lta (l)t b (2 ) - t-(2 )tb (l)L

V2 V 2
(4.12)

This also explains the l /\/2 factor in the spin wave functions given in Eq. (4.9).

E X A M P L E 4.2. Calculation of the energy of the helium atom using the normalized
wave functions (4.12).

S o lu tio n : The total hamiltonian operator for the helium atom can be written in the
form H = Hi + H2 + H i2, where

ft2 _2 2c2 , ft2 _2 2e2

Hi = — r — Vi — and H2 = — 5— V 2 — -------
2m 4jr «οΠ 2m Ijreor2

are the hamiltonians for each electron in the coulomb field of the nucleus and

Hi2 = e2/At ear1 2

corresponds to the interaction between the two electrons. N ote that

H,^a(t) = E „ t , ( i ) and » , t b ( i ) = l'-btb(i), * = 1, 2,

where E a and Eb would be the energy of each electron if its interaction with the other is
neglected. Therefore (Hi + H >)t — (/ία + Eb t , where t refers to either of the normal­
ized wave functions t s or t s defined by Eq. (4.12). Thus we may obtain the energy of
158 Atoms with many electrons (4.3

the helium atom by using Eq. (2.50); that is,

E — = Ε α -\-Ει,-\- [φ * Η ιΐφ dr.

A direct calculation, recalling the normalized forms of φ.ι and Φλ given in Eq. (4.12),
yields
= C ± AT,

where

C = I — I W D I 2 dr,hM2)|2 dr2
J l J 2 47Γ€0Π2
and

K = I -------------- φ *Α )Φ ιΟ ) ά τιφ Ι(2 )φ α(2) dr-2.

J i J 2 47rcori2
Therefore
E = E a A -E bA -C ± K .

W e sec therefore that we obtain two possible energy values corresponding, respectively,
to the symmetric wave function φα (positive sign) and to the antisymmetric wave func­
tion Φλ (negative sign). Since it can be shown that K is positive, the state described by
Φλ has lower energy than that corresponding to φ$ (the difference being 2K ), in agreement
with our previous intuitive discussion. The quantity C is called the coulomb integral; it
gives the interaction energy of the two electrons, assuming that they are distributed with
electric densities pi = —e|^a(l)|2 and p2 = —e|^6(2)|, respectively. The quantity K ,
called the exchange integral, gives the interaction energy of charges with densities

Pl = —Ρφ*(1)Φί(1) and p i = — €φΙ(2)φα(2).

This term has no classical explanation and is a pure quantal effect, resulting from the
identity of the electrons. 'Fhe evaluation of C anil K is a rather tedious process because
the variables are not separated due to the presence of the factor r j 2.

4 .3 Th v Exvluttion P r in v ip lv
T h e discussion o f helium and helium like atom s in the preceding section illustrates
the kind o f logic th a t must be applied in discussing m any-electron atoms. As a
reasonable starting point, let us again use the independent-particle m odel and con­
sider th at each electron m oves in the a ttra c tiv e electric field produced b y the
nucleus plus an average repulsive electric field due to the other electrons. T h e re ­
fore we can describe the dynam ical state o f each electron b y four quantum num bers:
n, I, nit, and ms * T h e first three quantum numbers g iv e the orbital m otion and the
fourth the orientation o f the spin. T h e energy o f the orb ital m otion depends on ly
on n and I, and thus each electronic state is identified b y the sym bol nl. AU elec­
trons havin g the same n l quantum numbers are called equivalent. T h e com plete
state o f the atom is specified by indicating the number o f equ ivalen t electrons in
each nl state. T h is constitutes w h at is called a configuration. I f there are x electrons

* In some atoms the spin-orbit effect is sufficiently strong to require the use of the quantum
numbers n, l , j , and m, instead. When this situation exists, it is called j - j coupling.
4.3) The exclusion principle 159

F ig. 4-5. Ionization energy of the elements as a function of atomic number.

in the state nl, this is indicated as nlc. F o r example, the ground-state configuration
o f helium is I s 2 and the first excited configuration is Is 2s.
The independent-particle m odel provides an excellent approxim ation when
combined w ith another principle, which we shall now explain. I t is w ell known
th at chem ical elements exh ibit certain regularities in their physical and chemical
properties. These properties repeat them selves in different elem ents in a m ore or
less cyclic form, and successive cycles or periods are com pleted a t the atom ic num­
bers Z = 2, 10, 18, 36, 54, and 86, corresponding to the (so-called) inert gases:
helium, neon, argon, krypton, xenon, and radon. In e rt gases are characterized
chem ically b y their v e ry weak or alm ost nonexistent cap ab ility for entering into
com bination w ith other elements. T h e p eriodicity in the properties o f the elements
is exem plified in a striking w ay b y the ionization energies, as shown in Fig. 4-5,
where w e see a trend which more or less repeats itself after each inert gas.
Chemists in the nineteenth century noticed this p eriod icity; in 1870 the Russian
scientist D m itri M e n d e lie v proposed his celebrated periodic classification o f the
elements in cycles or periods composed o f eight elements each. T h is classification,
however, did not w ork w ell and some elements, such as the transition elements and
the rare earths, did not fit easily into this sim plified scheme.
T h e regularities in the atom ic properties suggest certain regularities or periodici­
ties in the m otion o f the electrons in an atom . T o explain these regularities, the
Swiss physicist W o lfga n g Pauli (1900-1958) around 1925 proposed a new rule, since
called the exclusion p rin cip le. T h is principle not on ly explains the periodic physical
and chemical b ehavior o f the elem ents in a beautiful and simple manner but it also
correlates m any other im portant experim ental facts o f atom ic structure. Using the
independent-particle model, P a u li’s exclusion principle states th at

no Iu o electrons in an atom may have the same set o f quantum numbers.

160 Atoms with many electrons

T h is im portant rule is equivalent to the m ore general principle introduced in

Section 4.2 which stated that

Ilie total reave fu n ction o f a system o f electrons must be antisymmetric.

T h is m ay be considered as an altern ative and more general statem ent o f the exclu­
sion principle. A sim ple m athem atical consideration reveals th at the an tisym m etry
o f the w a v e function implies the v a lid ity o f the exclusion principle as expressed in
the first statem ent. H ow ever, the an tisym m etry o f the to ta l w a ve function is a
m ore general statem ent; it applies even if the independent-particle model is not an
adequate approxim ation.*
W e shall next illustrate a sim ple w a y o f w ritin g an antisym m etric function using
the independent-particle model. Assum e an atom w ith N electrons. L e t us desig­
nate b y a single le tte r (say a) alt the orbital and spin quantum numbers n, I, m,, m „
o f a given independent-particle state in the atom . T hen a configuration in which
one electron is in state a, another in state b, and so on, m ay be expressed by a
determ inan tal w ave function

M D M V * „ (3 )
M D 4ί ,(2) iM 3 ) (4.13)
V n ~\ i c (D ···

T h is w ave function is antisym m etric because, if we interchange tw o electrons (le t

us say I and 2), this is equ ivalent to interchanging tw o columns, and then the
determ inant changes sign. On the other hand, if tw o electrons have the same set
o f quantum numbers (say a == 6), the determ inant has tw o ident ical rows, and there­
fore is id entically zero. T h is shows the equivalence o f the tw o statem ents o f the
exclusion principle when the independent-particle m odel is used. T h e I / \ / A ! fac­
to r is for norm alization purposes only.
A s a concrete exam ple, let us consider the function ^..|Xs, where is given b y
E q. (4.12) and X*· b y E q. (4.9) w ith M s = I· Then

Ψ= * a* s = 4 = I M D M V - tM2)tMi)lx+ (i)x+(2)
V 2

I lM O x + d ) Φ „(2)Χ + (2 )
\/2 M i)x+(U M 2 )X + (2 )

T h is is a determ inant o f the ty p e o f E q. (4.13) w ith N = 2, except that the orbital

and spin parts o f the independent-particle w ave functions are shown separately.

* The principle of antisymmetry of the total wave function applies not only to electrons
but also to other fundamental particles, such as protons and neutrons. All particles
described by antisymmetric total wave functions, for reasons to be explained in Chapter 13,
are called fermions.
 Kleclroit ic structure of atoms lt il

4 .4 E U 'I-Iritni4' S l r u v l u r v o f A t o m s
W e shall now consider how we m ay use l ’ auli’s exclusion principle to determ ine the
electronic configurations o f atoms. L e t us first calculate the num ber o f com bina­
tions o f quantum numbers mi and m , th at are possible for each value o f the angular
m om entum I. T h is w ill g iv e the m axim um number o f electrons that can be accom ­
m odated in the state nl. W e know th at for each value I there are 21 + I values
o f mi, and for each I, mi pair we m ay have the electron w ith spin up or down
(m , = = t i). So the m axim um number o f electrons that can b e accom m odated in
a state nl w ith ou t v iolatin g the exclusion principle is 2(2/ + - I ) . T h is is indicated
e xp licitly in the follow in g table.

A n gu la r m om entum , /: 0 1 2 3 4
Sym bol: s p d f g
Occupation number, 2(2/ + I ) : 2 6 10 14 18

Then, in the building-up process o f the atom s from Z = I up to Z = 92 (and on ),

electrons occupy the low est-lying en ergy states available, each up to the m axim um
number allow ed b y the exclusion principle. Once an n l state has received its full
qu ota o f electrons, the next state begins to fill up.
T h e order in which the successive nl
states fill up is indicated in Fig. 4-6.
T h e re m ay be slight changes for some T o t a l num ber o f
I.c v c l lilectron s electrons at each
particular atoms, but in general the or­ designation in shell shell com pletion
der is as shown. W e observe in the first
7P---------------H j- I ------------ 118(?)
place certain "en ergy g a p s” ; th at is,
regions where the energy difference be­ f e = = 14 Η
7s' '" 2 J
tween tw o states or levels is much larger
Gp---------------------G- ) ----------------SG (R n )
than it is between levels below the low er S d ----------------- 10 -3 2
4 f- ------- ■H
or ab ove the upper. T h e en ergy gaps ap­ Gs' 2
pear between Is and 2s, between 2p and
S p ------------------- 6 ~ ) --------------- 54 (X e )
3s, 3p and 4s, 4p and 5s, and so on. E n ­ 4 d ----------------- t o M 8
ergy levels grouped between tw o energy 5s'------------------- 2 J

gaps constitute a shell * Each nl state 4 p ----------------- ------------------------------ 88

com posing a shell is called a subshell. 3 d ----------------- 10 r 18
4 s ------------------- 2 J
T h e m axim um number o f electrons in
successive com plete shells occurs pre­ 3 p -------------------® ~ l - 8 -----------------
3 s -------------------2 J 1
cisely at Z = 2, 10, 18, 36, 54, and 86,
which are the inert gases, as required by 2 p -------------------G~1 ----------------10 ( N e )

experim ental evidence. T h e re m ay be -------------------

another inert gas at Z = 118, but no 2 2 ----------------2 (H e )
atom with such a high number o f elec­
trons has been found in nature or y e t shell structure of atomic energy
made artificially. levels.

* Spectroscopiste also use the term shell to designate all states in many-electron atoms
Corresponding to the same n. In that sense, states with n = I, 2, 3, 4, . . . constitute the
K , L, Μ , .V, . . . shells. This is the same terminology used in Chapter 3 for one-electron
atoms.
T A B L E 4—1 Electronic C o n figu ratio n o f A to m s*

configuration
_o

energy, eV
rt

energy, eV
Ionization

Ionization
S ym bol

Ground

Ground
Z

S ym bol
Z
B φ S M
state
C Λ 2 =
O “ o 8
I H 2S Is 13.595 52 Tc 3P 2 4 d 111 5s2 5p4 9.01
2 He 1S Is 2 24.581 53 I 2P 322 4 d lu 5s2 5pa 10.454
54 Xe 1S 4 d '° 5s2 5p° 12.127
3 Li 2S [H e] 2s 5.390
4 He 1S 2s2 9.320 55 Cs 2S (X e ) Os 3.893
δ H 2P ir 2 2s2 2p 8.296 56 Ila 6s2 5.210
6 Is
C 3Po 2s2 2p2 11.256 57 La 2D 322 5d 6s2 5.61
7 N 4S 2s2 2p3 14.545 58 Ce 1G 4 4f 5d 6s2 6.54
8 O 3P 2 2s2 2p4 13.614 59 Pr 4Ie 22 4f3 6s2 5.48
9 F 2P3/2 2s2 2ps 17.418 60 Nd 5I 4 4f4 6s2 5.51
10 Ne 1S 2s2 2p° 21.559 61 Pm 6H j 22 4f5 6s2
62 Fm 7F,, 4f6 6s2 5.6
U Na 2S IN el 3s 5.138 63 Eu 8S 4f7 6s2 5.67
12 Mg 1S 3s2 7.644 64 Gd 9D 2 4f7 5d 6s2 6.16
13 Al 2P ir 2 3s2 3p 5.984 65 Tb 0H 15/2 4 f9 6s2 6.74
14 Si 3Po 3s2 3p2 8.149 66 Dv 5I 8 4 f '° 6 s 2 6.82
15
16
P
S
4S 3s2 3p3
3s2 3p4
10.484
10.357
67 Ho 411522 4 f " Os2
3P 2 63 Er 3Ho 4 f12 6s2
17 Cl 2P 322 3s2 3p5 13.01 69 Tm 2F i 22 4 f13 6s2
18 Ar 1S 3s2 3p6 15.755 Yb
70 1S 4 f14 6s2 6.22
71 Lu 2D 322 4 f14 5d 6s2 6.15
19 K 2S [A r ) 4s 4.339
72 Hf 3F 2 4 f14 Srl2 6s2 7.0
20 Ca 1S 4s2 6.111
73 Ta 4F 322 4 f 14 Srl3 6s2 7.88
21 Sc 2IXir2 3d 4s2 6.54
74 VV 6D 0 4 f14 5d4 6s2 7.98
22 Ti 3F 2 3 d 2 4s2 6.83
75 Re 6S 4 f14 5d5 6s2 7.87
23 V 4F 3i2 3d3 4s2 6.74
76 Os 5D 4 4 f14 Sd6 6s2 8.7
24 Cr 7S 3d5 4s 6.764
77 Ir 4Fo22 4 f14 Sd7 6s2 9.2
25 Mn 0S 3d5 4s2 7.432
78 Pt 3D 3 4 f14 5d8 6s2 8.88
26 Fe 5D 3 3d® 4s2 7.87
79 Au 2S [X e , 4 f14 5d‘ °J 6s 9.22
27 Co 4For2 3d7 4s2 7.86
80 Hg 1S 6s2 10.434
28 Ni 3F 3 3d8 4s2 7.633
SI Tl 2P l 22 6s2 6p 6.106
29 Cu 2S 3 d 10 4s 7.724
82 Pb 3Po 6s2 6p2 7.415
30 Zn 1S 3 d 10 4s2 9.391
S3 Hi 4S 6s2 6p3 7.287
31 Ga 2P ir 2 3 d 10 4s2 4p 6.00
84 Po 3P 2 6s2 6p4 8.43
32 Ge 3Po 3 d '° 4 s 2 4p2 7.88
85 At 2P 322 6s2 6p®
33 As 4S 3 d 10 4s2 4p3 9.81
.86 Rn 1S 6s2 6p° 10.745
34 Se 3P 2 3 d l u 4s2 4p4 9.75
35 Iir 2P 322 3 d 10 4s2 4p6 11.84 87 Fr 2S I Rn] 7s
36 Kr 1S 3 d 10 4s2 4p° 13.996 88 Ra 7s2
1S 5.277
89 Ac 2D 322 6d 7s2 6.9
37 Rb 2S [K r) 5s 4.176
90 Th 3F 2 6d2 7s2
38 Sr 1S 5s2 5.692
91 Pa 4K 1122 5f2 6,1 7s2
39 Y 2D 322 4d 5s2 6.377
92 U 5L 6 5f3 6d 7s2 4.0
40 Zr 3F 2 4d2 5s2 6.835
93 Np 6L u r2 5f4 6,1 7s2
41 Nb 6D 122 4d4 5s 6.881
94 Pu 7F 0 5f6 7s2
42 Mo 7S 4d5 5s 7.10
95 Am 8S 5f7 7s2
43 Tc 6S 4d5 5s2 7.228
44 Ru
I 96 Cm 9D 2 Sf7 6d 7s2
5F 5 4d7 5s 7.365
97 Hk (5 f8 6d 7s2)
45 Rh 4Fo22 4ds 5s 7.461
98 Cf (Sf0 Gd 7s2)
46 Pd 1S 4d‘ ° 8.33
99 E ( 5 f '° 6d 7s2)
47 Ag 2S 4 d 10 5s 7.574
100 Fm (5 f11 6d 7s2)
48 Cd 1S 4 d 10 5s2 8.991
101 Mv
49 In 2P i 22 4dl ° 5s2 5p 5.785
102 No
50 Sn 3Po 4 d 10 5s2 5p2 7.342
103 Lw
51 Sb 4S 4 d 10 5s2 5|)3 8.639

* Chemical symbols in brackets indicate the equivalent configurations of the remaining

electrons occupying filled shells. Configurations in parentheses are uncertain.
 Electronic structure of atoms 163

P s__________ |>

L L

H IIc
K t K

s p S P S |) S P

L t tl tl t tl t t
Li Bo B C
K tl tl tl tl
S 1> S I» S P S P

b t t t tl tl t t t l tl tl t tl t l tl tl
N O
tl I' Ne
K
tl tl tl
Fig. 4-7. Ground-state electronic configurations of the atoms of the first ten elements,
showing how they are built up.

T h e electron configuration o f the ground state o f the atoms o f the different chem ­
ical elements is given in T a b le 4-1.
I t is instructive to see in more detail how the first 10 elements are built up.
T h is is shown in the block diagram s o f Fig. 4-7. T h e s-subshells have one block
accom m odating tw o electrons w ith opposite spins, and the p-subshells three blocks
(m i = + 1 , 0, — I ) accom m odating six electrons. I t m ust be noted th at in filling a
p-subshell, w e have alw ays placed as m any electrons w ith parallel spins as possible.
T h is is because it is known experim entally that

the resultant spin of the (/round state o f atoms has the largest possible
value compatible with the exclusion prin ciple,

a result known as H u n d ’s rule. T h is prop erty can be explained as follows. We

know, from our discussion o f the helium atom , th at the ground state m ust be th at
state in which the repulsion o f the electrons is as small as possible, and this requires
a maximum an tisym m etry in the orbital part o f the w ave function. Since the to ta l
w ave function must be antisym m etric, we conclude th at the ground state corre­
sponds to the m axim um sym m etry o f the spin w a ve function, which occurs when
the spins o f the electrons are as parallel as possible.
T h ere are other interesting aspects th at are w orth m entioning in connection w ith
F ig. 4-7. F o r exam ple, hydrogen has a single ls-electron and lithium a single 28-
electron, but in the lithium atom the 2s-electron has availab le the rela tiv ely close
2p-levels as well as havin g a sm aller ionization energy (5.5 e V com pared w ith 13.6 eV
for h ydrogen ). These differences account for the distinct m etallic behavior o f
lithium, not exhibited b y hydrogen. S im ilarly, helium and b eryllium have com ­
plete Is- and 2s-levels, respectively. H ow ever, helium is an inert gas, while beryl­
lium is not. T h is is because one o f the 2s-electrons in the beryllium atom can be
excited to a nearby 2p-level, resulting in the excited state shown in Fig. 4-8, which
 Atoms with many electrons ('4.5

s p S P S I» S |)

I. t t L t t t L t t t I I t tl t t
K
tl Be* K
tl B* K
tl (·* K
tl N*

F ig. 4—8. Excited electronic configurations of beryllium, boron, carbon, and nitrogen.

corresponds to th e valence 2 observed in beryllium com pounds.* T h is excitation

requires an energy o f about 2.7 eV , w h ile in the case o f helium the m inimum excita­
tion energy is about 20 eV. Sim ilarly, in the case o f boron, the first excited state
m ay be obtained b y m ovin g a 2s-electron into a 2p-state, as shown in Fig. 4-8,
which requires an energy o f 3.6 eV. T h is state explains the trivalence o f boron.
T h e situation in the carbon, nitrogen, and oxygen atom s is more com plicated be­
cause new excited states can be produced b y reorien ting the spin and the orbital
angular m om enta o f the p-electrons. A particularly im portant excited state o f
carbon is shown in F ig. 4-8, which accounts fo r the let ravalence o f carbon in m any
o f its compounds.
W e m ay sum m arize our analysis b y saying th at the chemical and physical prop­
erties o f a chem ical elem ent depend on the ground-state electronic configuration
as w ell as on the nearby excited levels. F o r exam ple, w h at characterizes an inert
gas is that it is composed o f com plete shells and that, to excite one o f its electrons,
a com p ara tively large energy is required, due to the large energy gap separating
the last com plete level from the first unoccupied level. On the oth er hand, atom s
such as lithium , sodium, potassium, etc.— w ith Z = 3, 11, I!), . . .— are composed
o f closed shells plus one electron in the first level a b o v e the energy gap. So lithium
has a com plete K -shell and a 2s-electron; sodium has com plete K - and /./-shells and
a 3s-electron, and so on. T h is last electron is bound loosely and determ ines the
m etallic beh avior o f these elements. W h en the number o f electrons beyond the
last com pleted shells increases, the situation gets m ore and more com plex.

-i.!i Ms-S 4'oupling

T h e total angular m om entum o f an atom is a v e ry im portant p ro p erty because it
determ ines (am on g other things) the m agnetic properties o f the atom , and the
transition probabilities in rad iative processes. I f the atom is isolated, its total
angular m om entum is constant. W e shall designate it b y the quantum number ./
such that
J - = J (J + l ) h 2. (4.14)

T h e Z com ponent o f J is determ ined by the quantum number M such th at

Jz = Mh (4.15)
w ith
M = ± J , M -J - I ), · · · (4.1G)

* Valence and chemical binding will be discussed in Chapter 5.

/i.5) L -S coupling 165

T o each electronic configuration, there m ay correspond several possible values o f J ,

each associated w ith a d ifferent energy o f the atom. A n im portant problem o f
atom ic structure is the determ ination o f the allowed values o f J for each configura­
tion, and the corresponding w ave functions.
One m ethod o f m aking this determ ination is called the Ij - S or Russell-Saunders
coupling. Using the indepcndent-particle m odel w ith w ave functions given b y
E q. (4.13), in which each electronic state is characterized b y quantum numbers
n, I, mi, and m „ w e m ay first find the total orb ital angular m om entum o f the atom ,
such th at L = D t L i and L z = D t L „·. I f L and M t , are the quantum numbers
associated w ith L 2 and L z, then

L2 = L (L + I ) A2, Lz = M iA M l = ± L , ± (L - I ) ..........

(4.17)

w ith M I, = D t mu- T o a given configuration there m ay correspond several values

o f L , depending on the rela tive orientation o f the L i s. S im ilarly, the total spin o f
the atom is given by S = D t S i and S z == D> S zi. I f S and M s are the quantum
numbers associated w ith S 2 and S z, then

S2 = S (S + I )ft2, Sz = M s h, M s = ±S, M S - 1 ) , . · · ,

(4.18)

with M s = D .' msi· Again , to a given configuration there m ay correspond several

values o f S, depending on the relative orientation o f the Si’s.
Once L and S arc found, the total angular m om entum for the configuration is
given b y J = L + S. T h e possible values o f the quantum number J (w hich depend
on the rela tive orientation o f L and S ), arc

J = L + S , L + S — I , . . . , \L — <S|.
(4.19)

T h ese procedures are illustrated for three electrons in

F ig. 4-9. AU L i' s and S .’s are supposed to precess around
th eir resultants L and S, respectively. In turn, L and S
precess around J.
T h e state o f an atom is characterized by a set L , S, J
o f quantum numbers. States o f a configuration w ith the
same L and S constitute a term. Each term o f a configura­
tion has a d ifferent energy. T h e energy o f the different
terms o f a configuration m ust be obtained b y means of
rather elaborate m ethods, which w e shall not explain here.
B u t it is easy to recognize th at the energy o f a configura­
tion m ust depend on the value o f L . E ach value of L
corresponds to a different rela tive orientation o f the orbital
166 Atoms with many electrons

angular m om enta of the electrons, and therefore to a d ifferent rela tive orientation
o f their m otions. T h is must result in a different value for th eir coulom b or electric
interaction and thus in a different value fo r the energy o f the atom . States o f a
term having the same L - and S-values but different ./-values have p ractically the
same energy and constitute a m ultiplet. T h e sp litting o f an L -S term according to
the values o f J is a spin-orbit effect. N o rm a lly S < L ; therefore the total number
o f different J-valu es associated w ith an L -S term (called the m u ltip licity o f the
te rm ) is 2.S - f I.
Λ term is designated b y the sym bols S, P, D , F 1 . . . (depending on whether
L = 0, I, 2, 3, . . .) w ith a superscript to the left which denotes the m u ltip licity
25 + I ; th at is, a term is listed as 2 S + lL . Som etim es a subscript to the right, in­
dicating the value o f / , is added. T h e sym bol corresponding to the ground state
o f each o f the elem ents was indicated in T a b le 4-1.
L e t us consider some exam ples th at illustrate how to find the terms o f a con­
figuration. In the configuration (n s )(n 's ), which is composed o f tw o nonequivalent
s-electrons, w e must have L = 0, since I 1 = I2 = 0. T h e spins o f the tw o electrons
are either parallel or antiparallel, corresponding to S = I or S = 0, respectively.
In each case / = S. Thus the possible terms o f the (n s )(n 's ) configuration are
the trip let 3S i , and the singlet 1S 0. A s a second example, consider the configuration
(n p )(n 'p ) o f tw o nonequivalent p-clectrons. Since I i = I and I2 = I, the possible
values for the resultant orbital angular m om entum are L = 0, I, 2, g ivin g rise to
S-, P-, and D-states. In each state the spins m ay be parallel or antiparallel, which
gives S = I or 0. Thus the possible terms o f the (n p )(n 'p ) configuration are 1S,
3S, 1P 1 8P 1 1D , 3D .

T A B L E 1—2 T e rm s o f E qu iv alen t E lectrons

Config­ Config­
Terms Terms
uration uration

S 2S d, d9 2D
S2 1S d2, d s 1S1 1D, 1G, 3P 1 3F
P, P5 2P d3, d7 2P, 2D, 2F, 2G, 2H 1 4P, 4F
P21 P4 1S1 1D, 3P d4, d 6 1S1 1I), 1F, 1G, 1I, 3P, 3D 1 3F 1 3G, 3H 1 5D
P3 4S, 2P 1 2D d5 2S, 2P, 2I), 2F 1 2G 1 2II, 2I 1 4P, 4F 1 4D, 4G

W hen the electrons are equivalent, not all the term s are possible, due to lim ita­
tions imposed b y the exclusion principle. F o r exam ple, the configuration ms
adm its on ly the term 1S, as w e saw for the case o f helium. Look in g a t this exam ple
from a sligh tly different point o f view , we see th at in the m s2 configuration, if the
quantum numbers n, I, mi, and m , o f one electron are (n, 0 , 0 , + £ ) , those o f the
other m ust be ( « , 0, 0, — £), g ivin g A is = 0, w hich requires that S = O or a sin­
glet term. Sim ilarly for the wp2 configuration, the on ly possible terms are 1S, 1D,
and 3P. T h is is shown in K xam ple 4.3. T a b le 4 -2 gives the term s corresponding
to several configurations o f equ ivalent electrons.
 L -S coupling 167

One can easily find the ordering o f the terms in a configuration o f equivalent
electrons b y using tw o em pirical rules due to H u n d : ( I ) O f all possible terms,
those w ith the largest m u ltip licity (largest S ) have the lowest en ergy; o f all terms
w ith the same m u ltiplicity, the one w ith the lowest energy is th at w ith the largest
value o f L . (2 ) T h e ordering o f the m ultiplet levels o f each term w ill be norm al
(i.e., low est J has low est en ergy) when the subshell is less than h alf fu ll; the order­
ing is inverted if the subshell is m ore than half full. F o r exam ple, in the wp2 con­
figuration the levels in order o f increasing energy are 3P, 1D, and 1S and the trip let
3I5 is normal, w ith J = O the lowest, These rules are not rigorous and som etim es
are not followed.
C ou lom b S pin-orbit M a gn etic-ficld
interaction interaction interaction

*S

/
n p- /
is
1D2

3P1

F ig. 4—10. Energy levels of the np2-configuration. 3Po

T h e resultant average m agnetic m om ent o f an atom is proportional to J, which

means th at a substance composed o f single atom s w ill be param agnetic if J 0
and diam agnetic if J = 0. In the presence o f an external m agnetic field the energy
levels o f a state L S J are split into 2J + I sublevels, corresponding to the different
possible orientations o f the m agnetic m om ent o f the atom rela tive to the m agnetic
field, g ivin g rise to a Zeem an effect. Figure 4-10 shows the energy sp litting o f the
configuration np2 due to the several effects w e have m entioned.
A s an illustration o f the com p lexity o f excited energy levels o f m any-electron
atoms, Fig. 4-11 shows some o f the energy levels o f the carbon atom . T h e ground
configuration o f carbon is l s 2 2s2 2 p 2; the ground-state term is 3P, w ith nearby
excited term s 1D and 1S. Successive term s corresponding to the excitation o f one
o f the 2p electrons (g iv in g rise to configurations I s 2 2s2 2p ns, I s 2 2s2 2p np, and
Is 2 2s2 2p n d ) are shown in the first three columns. T erm s resulting from the
excitation o f one o f the 2s electrons, g ivin g rise to configurations I s 2 2s 2p 3 and
Is 2 2s 2p 2 3s, are shown in the last tw o columns. T h e sym bols shown at the top
o f each column correspond to the state o f the ion le ft when the excited electron is
rem oved. Incid en tally, the state 5S o f the configuration I s 2 2s 2p 3 corresponds to
the situation shown in F ig. 4-8.
F igure 4-12 shows some energy levels o f the oxygen atom . O xy g en ’s ground
configuration is I s 2 2s2 2p 4 ; the ground-state term is 3P, w ith nearby excited terms
1D and 1S o f the same configuration. T h e levels shown correspond on ly to the
excitation o f one o f the 2p electrons, resulting in configurations I s 2 2s2 2p 3 ns,
Is 2 2s2 2p 3 np, etc.
168 Aloms with many electrons

T h e large number o f availab le energy levels clearly shows th at the spectra o f

m any-electron atom s are much more com plex than the spectra o f one-electron
atoms. Several selection rules lim it the possible transitions. F o r electric-dipole
transitions the selection rules are the follow ing:

AL = ±1, AS = O,
AJ = 0, ± 1 ( n o O —> 0 ), (4.20)
A M = 0, ± 1 .

T h e possibility J = 0 —» J ' —> 0 is forbidden b y the law o f conservation o f angular

m om entum , since it can be shown that a photon has an intrinsic angular m om en­
tum or spin o f one unit (see Section 9.2). H ence it is impossible fo r there to be a
transition ./ = 0 —* ./ ' = 0 with emission (o r absorption) o f a photon carrying
 *#.1/ L -S coupling

2s- 2p3 ( 2P)

HS Hp

150 ( - 150.3(H) cm” ' ) ----- ^ ------------------------------ 18.50-

-
Zs2 2ICt (2I))
140 HS Hp H(I

( —136,540 e m -‘) 'M .___ ^ ___ ^ ____

7 1O O---- 10.93

(>— ' I ) - 1S
130
5------ ' I ) -I" - 1D
-Ip
4 3D
3D 2s 2p·’
4- 'l)
120
2s2 2p3 (4S) 'I ) - 1P
'I·· 3 ___
Hp nd 3=
·,—

HO '/////. _ _ _ m _____ m . L1H9^ o . ?

ο— 13.01
7 ----- 6-
«5 =% - 4= 3D , — 1D
100 - 3P 5D — 3I)
-S p 3D
. , - 3S 5I)
jS

i 90
% , -
3 3P
Sp

80
.. — 3S

70

IS (2s2 2p4)
30

20
1D (2s2 2p4)

10

0 3P (2s2 2p4)

F ig. -1-12. Energy levels of the oxygen atom.

Oil· J unit o f angular m om entum w ith ou t viola tin g the conservation o f angul;
me imentum. A ls o A M = 0 is n ot possible w ith A J = 0, because in this case aga
the i conservation o f angular m om entum requires a change in the direction of
«■V ich im plies a change in J 2, w ith a corresponding change in M .
170 Aloms with many electrons {0.0

T A B L E 1—3 Possible mi a n d m, V alu es for the np2 C o n figu ratio n

—I 0 +1
Ml \

+2 (I,+ ) ( ! , - )

(l,+ )(0 , - )
+ 1 (I , — ) (0, - ) ( I , + K O ,+ )
(I , - M O , + )

(l,+ )(- l, - )
0 (I , — ) ( — I, — ) (0 , + ) ( 0 , - ) (I,+ K - I , + )
(I,- K - I , + )

( 0 , + ) ( — I, - )
—I ( 0 , — ) ( — I, - ) (0, + ) ( — ! , + )
(0 , - K - I , + )

—2 ( — ! , + ) ( — I, - )

E X A M P L E 4.3. Analysis of the configuration np2.

S o l u t i o n : In this configuration, corresponding to I = I, the quantum numbers of the

electrons are (n, I, mi, m,) and (n, I, m\, m',). T o comply with the exclusion principle, the
two sets of quantum numbers must be different and therefore must differ either in mi or
m „ or both. The possible values for mi and m\ are + 1 , 0, — I, and those of m, and m'„
are + J or — J. T o simplify the notation, the spin values will be designated as plus ( + )
or minus ( — ) and the common quantum numbers » and / ( = I) will be omitted. Table 4-3
presents the 15 combinations of quantum numbers compatible with the exclusion prin­
ciple. Each entry gives a possible combination (mi, m,) and (m'i, m',). They are arranged
according to the common values of M l — m/ + m\ and M s — m, m',. Each set of
quantum numbers corresponds to a wave function of the type given by Eq. (4.13).
Figure 4—13(a), in which a method developed by J. C. Slater for analyzing configura­
tions is used, shows the number of different wave functions corresponding to each value
of M l and M s- From the table or the figure it may be seen that the largest value of M l

M,. M,. M,.

O — -U s

(d) L = O1S = D

Fig. 4-13. Slater method for obtaining the terms of the np2-configuration.
4.6) Atoms with one or two valence electrons 171

F ig . 4-14. Binding energy of inner electrons as a function of the atomic number.

is 2, and this must correspond to L = 2 or a D-term. The value M l = 2 is associated

with M s — 0 only, and must correspond to S = 0, making up a ’ D-term. This state
requires five wave functions with M l = 2, I, 0, — I, — 2, and M s = 0. These wave func­
tions are indicated in Fig. 4-13(b). The remaining ten wave functions are properly grouped
in Figs. 4-13(c) and (d ). Arrangement (c) contains all nine combinations of M i = + 1 ,
0, — I , with M s = + 1 , 0, — I, and therefore corresponds to a term with L = I and
S = I or 3P. Finally, in (d ), we have the last wave function, with M l — 0 and M s = 0,
which must correspond to a term with L — 0 and S = 0 or ’ S. Thus the only possible
terms of the np2 configuration are 1S, 1D 1 and 3P.

4 .Ii AiontH irith O n v o r T iro V a lv n v v E lv v tro n s

T h e general th eo ry o f a tom ic structure developed in the previous sections can be
illustrated in a v e ry sim ple w a y in th e case o f atom s com posed o f com plete shells
plus one or tw o electrons. T h e electrons fillin g the com plete shells constitute the
core or kernel and the rem aining electrons are called the valence electrons. T h e
binding en ergy o f the kernel electrons is higher than th at o f the valence electrons
and increases rap id ly w ith the atom ic number, as shown in F ig. 4-14. T h e figure
172 Atoms with many electrons

gives the binding energy o f Is, 2s, 2p, etc., electrons as a function o f the atom ic
number. Hence, the kernel electrons are rather tig h tly bound and remain prac­
tically undisturbed in m ost o f the processes in which the atom participates. I t is
the valence electrons th at are m ostly responsible for the chemical properties o f the
ato m ; these are the ones that participate in chem ical reactions and chem ical binding.
I t can be easily shown th at a com plete shell, filled w ith its full quota o f electrons,
necessarily has L = 0 and S = O . In other words a com plete shell, and b y exten­
sion the kernel, does not contribute either to the orb ital angular m om entum or to
the spin o f the atom . H ence the orbital angular m om entum and the spin o f the
atom are both due entirely to the valence electrons. F o r exam ple, in the case
o f one-valence-electron atoms, the spin o f the ato m is S = £ and all energy levels
in which on ly the valence electron is excited are doublets (2 S + 1 = 2). F o r these
atom s L = I , where I is the orbital angular m om entum o f the valence electron.
T h e sim plest single-valence-electron atom is lith ium ( Z = 3), which has an
ou ter or valence electron and Z — 1 = 2 electrons in the kernel. T h e tw o kernel
electrons occupy the level w ith n = I , havin g a configuration I s 2. I f the valence
electron m oves in such a w a y th at it does not penetrate the kernel, the effec­
tiv e field it perceives is th at o f the + 3 e charges o f the nucleus and the — 2e charges
o f the kernel, resulting in an effective charge o f + e . T h erefo re the m otion and the
energy levels o f the valence electron w ould be sim ilar to those found for the h yd ro­
gen atom. T h is, according to our discussion o f the w a v e functions in Section 3.5,
occurs on ly app roxim ately w h enever the angular m om entum is large. B u t for low
values o f the angular m omentum, and especially for the s-states (I = 0) the orb it
o f the valence electron is penetrating and extends through the kernel, even reach­
ing v e ry close to the nucleus.
Figure 4-15 shows the radial charge distribution o f the lithium kernel, togeth er
w ith the radial charge distribution o f the valence electron for the states 2s and 2p.
(T h e radial charge distribution is proportional to r 2[I? (r )]2; see F ig. 3 -1 3 .) We
thus see th a t the valence electron in its m otion spends some tim e w ith in the kernel,
the penetration being greater for an s-orbit than for a p-orbit. T h e effective charge
which the valence electron feels during its m otion in a penetrating o rb it goes from

r2[/f(r) I2

Fig. 4-15. Radial charge distribution of the kernel and of the valence electron in the
2s- and 2p-states in the lithium atom.
4.5) Atoms with one or two valence electrons 173

I Iy d ro gcn Lithiu m Sodium

F ig. 1-16. Energy levels of hydrogen, lithium, and sodium.

+ e when it is far out up to + 3 c , when it has penetrated deep into th e kernel. T h e

corresponding energy is interm ediate between th at o f hydrogen ( Z = I ) and o f
L i 2+ ( Z = 3). Since the penetration depends on the angular mom entum , the energy
o f the valence electron also depends on the angular momentum. T h e sm aller the
angular m omentum, the low er (m ore n egative) the energy; i.e., the greater the
penetration. So instead o f the le v el scheme shown in Fig. 3-8, in which all states
having the same n have the same energy irrespective o f their angular m omentum,
w e have the situation d epicted in F ig. 4-16, fo r the one-valence-electron atom s
lithium and sodium. T h e en ergy levels o f hydrogen are also shown for comparison.
W e see th at the larger the value o f n and o f the angular m om entum I, the closer
the energy levels o f lithium and sodium are to those o f hydrogen, because the
orbits are less penetrating and the effective coulom b field corresponds to Z = I.
H ow ever, the m ore penetrating orbits h ave energy levels th at are qu ite distinct
from those o f hydrogen.
T h e possible transitions o f the valence electron are regulated by the selection
rules (3.17), resulting in the follo w in g spectral series:

Sharp series: ns —» ?i'p,

Principal series: np —* n's,
D iffuse series: nd —> n'p,
B ergm ann series: » f —» » 'd ,
17U Atoms with many electrons (4.S

-7 X 1 0 -+ V

1= 0 I / 2
4—
5S|/2 £24 2 ± 3Ds/2 I
4P>'2 ' 3 l ^ T 6><10' eV
3—

2— ~ 2 X H H cV
3P|/2 T

Fig. 4-17. Fine structure of the energy I-

levels of the sodium atom due to the
spin-orbit interaction.
0—1
3t5|/2

.S = O S =I

Fig. -I—18. Energy levels of calcium, showing some transitions.

5.6) Atoms with one or two valence electrons 175

and so on. D ue to the spin-orbit interactions, all energy levels shown in Fig. 4-16
(except the s-levels) are doublets, w ith a separation proportional to S - L . Thus,
for example, the actual energy levels o f sodium, in which on ly the valence electron
is excited, are as shown in F ig. 4-17.
In the case o f atom s w ith tw o valence electrons, the situation is v e ry sim ilar to
th at o f the helium atom. T h e resultant spin o f tw o electrons can be either 0 or I,
and the energy levels fall in tw o groups, singlets (S — 0) and triplets ( S = I). The
singlets correspond to the tw o valence electrons w ith their spins antiparallel, and
the triplets to the tw o valence electrons w ith th eir spins parallel. T h is is the case
o f atom s such as those o f beryllium , magnesium, calcium, etc. F igu re 4-18 shows
the energy levels o f the calcium ato m ; these correspond to the situation in which
only one valence electron is excited. Since in the ground state o f calcium the
valence electrons have the configuration 4s2, the excited states correspond to
4s nl, w ith n = 4, 5, 6, . . . T h e values n l o f the excited electron are shown a t the
176 Atoms with many electrons

top o f the figure. Som e o f the possible transitions are also shown. T h e y must con­
form to the selection rules (3.17). T h e tw o clashed lines are transitions from a
trip let to a singlet state; th ey v io la te the selection rule A S — 0, and are therefore
v e ry weak.
O f course there is the possibility o f excitin g both valence electrons and this gives
rise to new energy levels, as illustrated in F ig. 4-19 for beryllium , which has the
ground-state configuration Is 2 2s2. T h e first three columns correspond to excita­
tion o f on ly one valence electron, as in F ig. 4-18 for calcium, and the configurations
are I s 2 2s ill. T h e rem aining three columns correspond to the case in which one
valence electron has been excited to the state 2p and the other to nl, so th at the
configurations are I s 2 2p nl. O f course, m any m ore excited states exist.
T h is analysis o f atom s w ith one and tw o valence electrons should suffice to dem ­
onstrate the m any com plexities in volved in an alyzing atom ic structure.

/. 7 X -K a y S pvvtra
So far we have considered on ly excitations o f the valence electrons, which result in
w h at is usually called the optical spectrum. B u t it is possible to excite the electrons
which fill the com pleted shells o f the kernel. These excitations are responsible for
the characteristic x-rays em itted or absorbed by atoms.
F'igurc 1-14 g a v e the intensity distribution as a function o f the w avelength for
the brem sstrahlung from the anticathode in an x-ray tube m ade o f m olybdenum ,
fo r several applied voltages. W hen the v o lta ge is increased, certain v e ry sharp
peaks o f inten sity o f x-rays are observed, corresponding to w ell-defined w a v e ­
lengths. In F ig. 1-14 the peaks first appear when the applied v o lta g e is 25 kV.
(T h e actual excitation volta ge is 20.1 k V .) T hese peaks arc called characteristic
x-rays. T h e w avelengths o f the peaks are independent o f the applied v olta ge, but
depend on the m aterial o f the cathode.
C haracteristic x-rays have a sim ple explanation. W h en the electrons in the x-ray
tube strike the target, th eir energy m ay be sufficient to knock one o f the elec­
trons out o f the kernel. Suppose the ejected electron is in the -shell. W hen a
K -electron is rem oved, an e m p ty state (o r hole) is le ft in the /f-shell. A n oth er
electron in a higher energy level o f the kernel (o r perhaps a valence electron, or
even a free electron) m ay fall into the vacan t state in the K ·-shell. Since the am ount
o f energy in vo lved is fairly large, the radiation em itted b y the electron falling into
the vacant state lies in the x-ray region o f the spectrum. T h e electron falling into
the vacant state o f the Λ -shell m ay proceed from the L , Μ , N , etc., shells and
therefore we have a series o f x-ray iines designated K a, K g, K y, etc. I f the vacant
state is in th e L-shell, the electrons m ay fall from the M , N , etc., shells g ivin g rise
to the L a, Lg, etc., x-ray lines, and so on. T h e x-ray transitions in an ato m with
Z ~ 36 are illustrated schem atically in F ig. 4-20. N o te th a t x-ray emission is possi­
ble on ly if a vacancy is produced in an inner shell, since the exclusion principle
prevents a transition from a higher level into a low er, but fu lly occupied, shell.
T h e vacant space in an inner shell m ay also be produced by absorption o f radia­
tion, resulting in a photoelectric effect for electrons o f the K , L , M , etc., shells.
 X-Ray spectra 177

3 -1

λ;.1/2
-hl/2 3s

I II. .2I V
Il- 1/2-
I-
—r~ —1 2Si n
La

--Si

Ka Ku Removed
electron

Fig. 1-20. X-ray transitions in an Fig. -1—21. Fine structure of x-ray tran­
atom with an atomic number Z ~ 36. sitions.

A ctu a lly, x-ray transitions are m ore com plex than one w ould gather from
F ig. 4-20, because the energy released depends on the initial and final terms.
F o r example, when a Is electron is rem oved from the //-shell, the en ergy o f the
ion produced is unique. B u t if the electron is from a full /.-shell, it m ay be a 2s
or a 2p electron. In the first case the configuration o f the electrons th at rem ain
in the shell is 2s 2p°, corresponding to a state 2S i/2, but. in the second case the
configuration o f the electrons th at remain in the shell is 2s2 2p 5, corresponding to
the states 2P 1/* or 2P 3/2- T h erefo re there are three possible states o f the L-shcll
minus one electron, each w ith a d ifferent energy. F o r the /!/-shell minus one elec­
tron there are five possible states, and so on. T hese states and som e o f the result­
ing x-ray transitions are shown in F ig. 4-21. T h u s K a and K tj lines are doublets,
the L a line is com posed o f eight close lines, and so on.
T h is fine structure o f the energy levels is also reflected in the coefficient o f linear
absorption for the photoelectric effect. In F ig . 4 -22 w e can see that a definite
m inimum energy E r is required to ionize an atom b y extractin g a A'-electron.
B u t if an /,-electron is rem oved, there m ay be three possible ionization energies
E l i, E lu ,E l u I, depending on the state in w hich the shell has been left. S im ilarly,
there are five ionization energies if the electron proceeds from th e .!/-shell, and so
on. T h is means that when electrom agnetic radiation falls on a m aterial, the
linear absorption coefficient or m acroscopic cross section S fo r the photoelectric
effect (Section 1.9) varies as a function o f the energy o f the radiation, as shown in
178 Atoms with many electrons (4.7

Fig. I—23. Variation of the linear

absorption coefficient for x- and
Ύ-rays as a function of the photon
energy.

Fig. 1—22. Transitions resulting

from the absorption of x-rays;
this absorption is accompanied
elect ren by electron emission.

F ig. 4-23. T h e re is a general trend in w hich 2 decreases as the photon energy in­
creases or the w avelength decreases. W hen the photon energy falls a b o v e the
m inim um value required to extract an L-electron, a sudden increase in the value
o f 2 occurs, since there are now m ore electrons w ith which the photons m ay interact;
o n ly in this case there are three closely spaced peaks, corresponding to E l i, E l ii,
and E L iu , respectively. W hen the photon energy falls ab ove the valu e Ε κ , there
is another sharp increase in the valu e o f 2 because the photons have enough energy
to eject a K -electron. These sudden changes in 2 are called absorption edges. T h e
if-ab sorp tion edge for lead was also illustrated in Fig. I —19. N o te that, in general,
the energies (o r w avelen gth s) in vo lved in x-ray emission and absorption are not
e x a c tly the same because the energy levels in vo lved are different. B oth x-ray
absorption and x-ray emission are v e ry useful tools w ith which to gath er inform a­
tion abou t the inner shells in an atom .
In some cases the photon em itted in an x-ray transition is absorbed b y another
electron o f the same atom , which is therefore ejected as a result o f an internal
photoelectric effect. T h is process o f internal conversion o f x-rays into p h o to­
electrons is called the A u ger effect.
 Problems 179

R eioren crn

1. “ Spectra Inform Us About Atom s,” W . Meggers, The Physics Teacher 2, 303 (1964)
2. “ Basic Concepts of Self-Consistent Field Theory,” S. Blinder, Am. J . Phys. 33, 431
(1965)
3. “ Terms Obtained from Configurations of Equivalent Electrons,” E. Tuttle, Am. J.
Phys. 35, 26 (1967)
4. “ Physical Basis for Hund's Rule,” N . Karayianis, Am. J. Phys. 32, 216 (1964) and
33, 201 (1965)
5. “ H. G. J. M oseley,” L. Redman, The Physics Teacher 3, 151 (1965)
6. “The Scientific Career of Charles Barkla,” R. Stephenson, Am. J. Phys. 35, 140
(1967)
7. Atomic Spectra and Atomic Structure, G. Herzberg. N ew Y ork : Dover, 1955, Chapters
I and 2
8. Atomic Spectra, R. Johnson. New Y ork: John W iley, 1950
9. The Behavior of Electrons in Atoms, R. Hochstrasser. New Y ork: Benjamin, 1965
10. Elements of Wave Mechanics, N. M ott. Cambridge, England: Cambridge University
Press, 1962, Chapter 5, Sections 2.2, 2.3, 4.5, and 4.6
11. Structure of Mailer, W. Finkelnburg. N ew Y ork: Academic Press, 1964, Chapter 3,
Sections 8 and 11-17
12. Quantum Theory of Matter, J. Slater. New Y ork: McGraw-Hill, 1951, Chapters 6 and 7
13. .4 Source Book in Physics, W . Magie. Cambridge, Mass.: Harvard University Press,
1963, page 600 (Roentgen)
14. Atomic Spectra, W . Hindmarsh. New Y ork: Pergamon Press, 1967
15. Principles of Modern Physics, R. Leighton. N ew Y ork: M cGraw-Hill, 1959, Chapters
7 and 8

ProbIeniH

4.1 The energy levels of heliumlike atoms,
when one electron is in the ground state
(n = I ) and the other in an excited state
(n > I ), could be expressed by
... RhcfZ - I ) 2
h — '- R h c Z 2 — x--------
n the wave function in determinantal form
This expression assumes that the electron
in the ground state fully screens one nu­
clear charge. Discuss the plausibility of
this expression. Compute the energy
levels for helium when n = 2, 3, and 4,
and compare with the experimental result.
W hy does the accuracy of the above ex­
pression for E increase when n increases?
4.2 Write, in determinantal form, the
three wave functions ^ s Xa of Eq. (4.10).
N ote that the wave function for M s = 0
consists of two determinants.
4.3 The ground state of lithium has the
electron configuration Is 2 2s. Write out
for the state when M s =
4.4 For the p2 configuration (see
Table 4-2), write the determinantal wave
functions corresponding to M l = 2,
M s = 0 and M t = I, M s = I.
4.5 Consider a three-electron system in
an sp2 configuration in the one-electron
approximation. Write the total wave func­
180 Atoms with many electrons
tion in determinantal form so that the
wave function corresponds to M l = I and
Ms = i
4.6 Given that the electron configuration
of an atom is 4s 4p 3d, write all possible
wave functions which correspond to M l -
I and M s = \. Use the determinantal
form.
4.7 Find the ground-state configuration
for the following atoms: (a) Si; (b) M n;
(c) Rb; (d) N i. Also write their ground-
state term.
4.8 Determine the ground-state configura­
tion and the number of unpaired electrons
in the following atoms: (a) S, (b) Ca,
(c) Fe, (d) Br.
4.9 (a) Show, on a diagram similar to
Fig. 4-7, the occupied states for the atoms
of Si, Cl, and As when they are in their
ground-state configuration. (b) Write
the electron configuration and the ground
terms of each.
4.10 Calculate the angle between the
total and orbital angular momentum for
the 4D 3/2 state.
4.11 Find the terms for the following con­
figurations and indicate in each case which
term has the lowest energy: (a) ns, (b) np3,
(c) (np2)(n 's), (d) np5, (e) (nd2)(n 'p ),
(f) (nd)(n 'd ).
4.12 List all the possible radiative transi­
tions for oxygen (see Fig. 4-12) when the
excited configuration is 2s2 2p3 ( 2D) 3d
( 3G).
4.13 Look at Figs. 4-11 and 4-12. Draw
some of the possible transitions compatible
with the selection rules. Determine the
wave numbers of these transitions and
check with experimental values, which
may be found, for example, in the Hand­
book of Chemistry and Physics.
4.14 Calculate the terms for np3 con­
figuration.
4.15 Give the S-, L-, and 7-values for the
terms 1S0, 2S p 2, 'P r , 3P 2, 3F 4, 5D 1, 1D 2,
and 0Faz2.
4.16 Find the terms corresponding to the
configuration nd2. A pply your result to
determine the ground and first excited
state of titanium.
4.17 Show that a complete nl shell must
necessarily have L = S = O.
4.18 T w o equivalent p-electrons have
strong spin-orbit coupling. Find the pos­
sible values of the resultant angular
momentum J if the problem is considered
as j - j coupled. Repeat the problem, con­
sidering L -S coupling. Does the same
value of J appear the same number of
times in each case?
4.19 In L -S coupling, one can obtain the
magnetic moment of an atom as IWave =
— (e/2mc)g j, where J refers to the total
angular momentum of the atom and g is
given by Eq. (3.40), with I, s, and j re­
placed by L, S, and ./. Find g for calcium
and aluminum. Discuss the splitting of a
3p term under the action of a weak mag­
netic field. Find the splitting if the mag­
netic field is strong.
4.20 Discuss the Zeeman effect under weak
and strong magnetic fields for the transi­
tions 3F —> 3D and 1F —> 1D in calcium.
4.21 The 4 1D 2 —►4 l Pi transition in cal­
cium yields a single line at 6439 A. What
wavelengths are observed if cadmium is
placed in a magnetic field of 1.40 T ?
4.22 The relative separation between the
different levels of an L S J multiplet due
to the spin-orbit interaction can be con­
sidered as proportional to S - L . Apply the
relation to the 3F and 3D multiplets. Draw
the energy levels of each multiplet and in­
dicate, by arrows, the allowed 3F —» 3D
transitions.
4.23 Repeat the preceding problem for
the case of 4D —* 4P and 4P —> 4S tran­
sitions.
4.24 Using the values given in Fig. 4-17,
calculate the wavelength separation of the
sodium D-lines. From the result, estimate
the constant a in E s l — aS · L for the
3 2P states.

4.25 Analyze the 3 2D —» 3 2P transition
in sodium. Determine the wavelength
separation, if any, for this transition.
4.26 Compute the energy, in electron
volts, of “red” (6500 A ) and of “ blue”
(4000 A ) photons. Using the energy scale
on Fig. 4-18, determine which of the sin­
glet and triplet transitions for calcium are
in the visible range of the spectrum. Com­
pare your rough estimates with a table of
wavelengths.
4.27 An expression which fits the energy
levels of the valence electron for one-
valence-electron atoms is
E n = - R h c ( Z — S )2/(n - δ)2,
where S is the screening constant and δ is
the quantum defect (which depends on the
n and I values of the particular valence
electron). Values of δ for lithium and
sodium are:
S P d and silver.
Li (Z = 3) 0.40 0.04 0.00
N a (Z = 1 1 ) 1.37 0.88 0.01
For S, one takes a value equal to the num­
ber of electrons in the kernel. Find the
energy of the ground state and the first
two excited states of the valence elec­
tron in lithium and sodium. [H in t: See
Fig. 4-16.]
4.28 The transition from the 3)>-level to
the 3s-level of sodium results in a line with
a wavelength of 5890 A . (W e ignore the
doublet structure.) Compute the wave­
length, using the values of the energy levels
given by the expression in Problem 4.27,
and compare with the experimental value.
Repeat for the 2p —* 2s transition in
lithium.
4.29 From the information contained in
Fig. 4-14, estimate the energy of the A -
and /.-absorption edges for aluminum and
oxygen. Plot the x-ray absorption curve
for these two substances in that region.
Problems 181
4.30 The following AVlines have been
measured;
magnesium: 9.87 A ; sulfur: 5.36 A ;
calcium: 3.35 A ; chromium: 2.29 A ;
cobalt: 1.79 A ; copper: 1.54 A ;
rubidium: 0.93 A ; tungsten: 0.21 A .
Plot the square root of the AVfrequency
against the atomic number of the element.
A young graduate student of Ernest
Rutherford’s, by the name of H. G. Mose­
ley found, in 1912, an empirical relation­
ship of the form V v = A (Z — c). (This
relation served to clarify the concept of
atomic number.) From your plot, verify
this relation and estimate the values of A
and c. Develop an explanation for this
relation of Moseley’s.
4.31 Calculate the wavelengths and ener­
gies for the K a x-ray lines of aluminum,
potassium, iron, nickel, zinc, molybdenum,
Compare the energy values
with those shown in Fig. 4-14. Use the
Moseley function of the previous problem.
4.32 The AV lin e for cobalt is 1.785 A .
What is the energy difference between the
Is- and 2p-orbitals in cobalt? Compare
with the energy difference between the Is-
and 2p-orbitals in hydrogen (i.e., the first
Lyman line). W hy is the difference much
larger for cobalt than for hydrogen?
4.33 (a) The A-absorption edge for tung­
sten is 0.178 A and the average wavelengths
of the A-series lines are K a = 0.210 A ,
Κβ = 0.184 A , and K y = 0.179 A . Con­
struct the x-ray energy level diagram for
tungsten similar to that in Fig. 4-20.
(b) What minimum energy is needed to
excite the A-series for tungsten? Deter­
mine the wavelength of the A0-Iine.
4.34 The Αχ-absorption edge in tungsten
is 1.02 A . Assume that a A„-photon is
absorbed by one of the 2s-electrons in an
Auger process. Determine the velocity of
the ejected photoelectron.
 5
MOLECULES

5.1 Introduction
5.2 The Hydrogen M olecule Io n
5.3 M olecular Orbitals o f D ia tom ic Mo
5A Electronic Configuration o f Some D iatom ic Molecules
5.5 Polyatom ic Molecules
5.6 Conjugated Molecules
5.7 M olecular Rotations
5.8 M olecular
5.9 Electronic Transitions in Molecules
5.10 Conclusion
5.2) The hydrogen molecule ion 183

5.1 In tro d u ctio n

An im portant problem related to the structure o f m atter is the structure o f m ol­
ecules. W h y do carbon atom s com bine w ith four hydrogen atoms, form ing m eth­
ane, but never w ith three or five hydrogen atom s? W h y is the C O 2 m olecule linear,
while H 2O is bent and N H 3 is a pyram id ? W h y does benzene ( C 6H 6) have the
form o f a hexagon w ith all hydrogen atom s in the plane? H ow can hydrogen atoms
join togeth er to form the m olecule H 2 but never form H 3? W h y are the spectra of
molecules so com plex when com pared w ith atom ic spectra, ranging from the m icro­
w ave up to the u ltraviolet? These and m any other questions could not be answered
satisfactorily before the quantum th eory was developed. One o f the m ost spec­
tacular successes o f the quantum th eo ry is the answers it provides to m any o f the
questions physicists and chemists h ave been asking about m olecular structure.
W e cannot say, however, th at our v ie w o f m olecular structure is a closed chapter
of physics.
L e t us begin our study o f m olecules b y asking ourselves: W h a t is a m olecule?
Th e first impulse is to say th at a m olecule is a group o f atom s bound togeth er by
some kind o f interaction. B u t this im m ediately raises new questions. D o the atoms
conserve their in d ivid u ality? H o w is the m otion o f the electrons affected when a
molecule is form ed? W h a t kind o f interaction gives rise to a m olecule? W e m ay
also adopt an opposite v iew b y saying th at a m olecule is a group o f nuclei sur­
rounded b y electrons in such a w a y th at a stable arrangem ent is produced. T h is is
the natural extension o f the concept o f an atom, which is a nucleus surrounded by
electrons. T hen instead o f looking at the H 2 m olecule as tw o hydrogen atoms, w e
m ay consider it as tw o protons and tw o electrons arranged according to the laws
of quantum mechanics and held togeth er b y electrom agnetic forces. F ro m a struc­
tural point o f v ie w this second approach is more fundam ental than the first.
H ow ever, as it is in m any cases, an interm ediate position is the m ost convenient.
W hen tw o atom s com bine to form a m olecule, the m ore tig h tly bound, or inner,
electrons o f each atom (w hich fill the com plete shells o f their respective kernels)
are p ractically undisturbed, rem aining attached to th eir original nuclei. O n ly the
outermost, or valence, electrons in the unfilled shells are affected and th ey m ove
under the resultant forces o f the ions, com posed o f the nuclei and kernels, as w ell
as their m utual repulsion. T h ese valence electrons are responsible for chem ical
binding and for m ost physical properties o f the molecule. T h is interm ediate posi­
tion is the m odel w e shall ad op t in this chapter; it is an excellent approxim ation
for analyzing m olecular structure.

5.2 T h e H y d r o g e n H loieeule Io n
Th e simplest o f all m olecules is the hydrogen m olecule ion H 2", consisting of
tw o protons and one electron. Chem ists w rite the form ation o f this m olecule as
H + H + —* H 2-, where H + is just a proton. In other words, the H 2" m olecule is
formed when a hydrogen atom captures a proton. B u t once the H 2" m olecule is
formed, it is no longer possible to tell w hich is the hydrogen atom and which is the
18k Molecules (5.2

—e
,Λ
\
\
\
\ r2
\
\
\
\

F ig . 5-1. The H j molecule ion. ^ r

proton. Our picture o f this m olecule is th at shown in F ig. 5 -1 : an electron m ovin g

in the electric field o f tw o protons w hich are separated a distance r.
W e m igh t say th at the electron does not rem em ber which proton it in itially be­
longed to. T h is lack o f m em ory is clearly revealed b y charge-exchange collisions.
Suppose th at the electron is in itia lly associated w ith proton P 1, and proton p 2
approaches the hydrogen atom from the righ t from a large distance (F ig . 5 -2 ).
In the region o f closest approach the m olecule lasts on ly a short tim e and then
breaks apart. W h en this happens there is a certain p ro b ab ility th at the incoming
proton w ill tak e the electron w ith it. Thus w e m ay w rite the process as

H+ + H (elastic collision),
/
H + + H —» H 2-
\
H + H + (charge-exchange collision).

T h e rela tive prob ab ility o f the tw o processes shown ab ove can be calculated as a
function o f the energy o f the incom ing proton. T h e result checks well w ith experi­
m ental evidence.
H H+ HJ

II

I>2 1>2
(c) (d )

F ig. 5-2. Collision of a hydrogen atom (H ) and a proton( H +), as seen in the CM frame
of reference, (c) Elastic collision, (d ) Charge-exchange collision.
5.2) The hydrogen molecule ion 185

T o discuss the stationary states o f the H J m olecule, we first assume th a t the

two protons are a t rela tive rest, and set up Schrodinger’s equation w ith a potential
energy

Ep = / - ( - (5.1)
” Aire 0 \ rl r2 r) '

Th e first tw o term s in the parentheses g iv e the a ttra ctive poten tial energy between
the electron and the tw o protons, and the third term is the repulsive poten tial
energy between the tw o protons. T h e variation o f the electronic poten tial energy
along the line jo in in g the tw o protons is shown in Fig. 5-3. I t resembles the double
potential w ell considered in Section 2.8 in connection w ith the N H 3 molecule.

Fig. 3-3. Potential energy along

the line joining the two nuclei in
H j and H 2.

T h e solution o f Schrodinger’s equation for H 3-, w hich is rather com plex, w ill be
sketched in E xam ple 5.2. A t the m om ent, however, we shall follow a m ore intu itive
reasoning. F irst w e shall consider the situation in which the electron is initially
orbiting around proton P 1, form ing a hydrogen atom in its ground state Is, and
the proton p 2 (o r H + ) is a t the right, v e ry far away. T h e w a ve function o f the
electron is practically undisturbed by proton p 2. Thus it coincides w ith the hydro­
gen ls-function drawn in Fig. 3-9. T herefore, if we draw the electron’s w a ve func­
tion along the line join ing the tw o protons as a function o f the distance from p i,
we obtain the curve shown in Fig. 5 -4 (a ), w hich shows that the electron is to be
found predom inantly around proton p i. Suppose now th at the electron is ini­
tially orb iting around proton p 2, form in g a hydrogen atom in the ls-state, and
that proton p i is far to the left. T h en the w ave function o f the electron is as shown
in Fig. 5 -4 (b ).
As the separation between the tw o protons decreases, the w a v e function o f the
electron is disturbed because the approaching proton (p 2 in F ig. 5 -4 (a ) and P 1 in
Fig. 5 - 4 (b )) tries to pull the electron aw a y from the other proton. T h e sym m etry
of the electron’ s potential energy shown in Fig. 5-3 suggests th at the prob ab ility
distribution o f the electron m ust exh ibit the same sym m etry. Thus, once the H 2
molecule is form ed, the electron w a v e function must have pronounced peaks around
each proton, where the poten tial energy is less, according to F ig. 5-3. T h e tw o
possible w ave functions for I I J which have the required sym m etry for their prob­
ab ility distribution are shown in F ig. 5 -4 (c ) and 5—4 (d ). T h e w ave function in
(c ) is even and in (d ) it is odd relative to the center, 0 , o f the m olecule. These
w ave functions w ill be designated as ^ ovon and Ψ,,μ , respectively. W c can express
186 Molecules (5.2

1A1
( a)
I >2

< l> )
IM

F ig. 5—i. Even and odd molecular orbitals in H j .

either w a v e function in an approxim ate w a y b y linearly com bining the hydrogen

w a ve functions (o r atomic orbitals) Ψι and Ψ2 corresponding to an electron orbiting
around either proton, designated by I and 2. Thus

lAcvcn ~ + Φ 2. ^odd ~ Ψ ΐ — Ϊ 2 · (5.2)

T hese w a v e functions are called molecular orbitals, ab b reviated M O . T h e theory

we are d evelopin g for w ritin g the m olecular orbitals is called the linear combination
o f atomic orbitals, abb reviated L C A O .
T h e states corresponding to m olecular orbitals and Ψ,,μ o f F ig. 5-4 are
designated, for reasons to be given later, a ^ sls and σ „ Is. T h ese states must have
different energies, as we can see from the follow in g explanation. B oth w a v e func­
tions g iv e m axim um p ro b ab ility for finding the electron near either proton, but
^even has an appreciable valu e in the region between the protons, while Ψ,,μ is v e ry
small (o r zero) in that region, as depicted in F ig. 5-5. F igu re 5 -5 (a ) shows the
variation o f the p rob ab ility density o f the electron along the line join ing the tw o
protons; Fig. 5 -5 (b ) shows the contour lines o f equal p rob a b ility on a plane passing
through the tw o protons, and in F ig. 5 -5 (c ) the shading indicates the relative
p rob ab ility o f finding the electron at d ifferent places.
W h en the electron is in the region between the tw o protons, it pulls the protons
together, offsetting their electric repulsion. W hen the electron is on either side, it
helps to separate the tw o protons. In other words, when the electron is in the
region between the protons, it acts as a "c e m e n t” holding them and results in a
stable configuration. In term s o f energy, we m a y say that the state σ ^ ΐζ cor­
responding to ^cvcn has a low er energy than σ „ 1β corresponding to ψ0<Μ· N o te the
sim ilarity between our discussion o f the w ave functions o f H j and our discussion
o f the double poten tial w ell in E xam ple 2.7.
5.2) The hydrogen molecule ion 187

F ig . 5-5. Probability density for even and odd molecular orbitals in . (a) Dis­
tribution along the lines joining the protons; (b) and (c) distribution in a plane containing
the two protons.

T h e difference in energy between states a 0ls and σ „ Is depends on the separation

of the tw o protons. Suppose w e start w ith a hydrogen atom and a proton H + far
apart. A s the distance between them decreases, we get tw o differen t energies for
each distance; one corresponding to S ta te a 0Is or w a v e function ^ rvfn and another
to S ta te a uIs or w a ve function ^ 0<ι<ι· Since the negative a ttra ctive poten tial energy
o f the electron dom inates the positive repulsive poten tial energy o f the proton in
state a „ls , the net energy decreases as r decreases. T h e reverse occurs for a uIs
and the net energy increases when r decreases. H o w ever, for distances sm aller
than a certain value r 0, the protons are so close that even in state a 0ls their repul­
sive potential energy begins to dom inate the a ttractive poten tial energy o f the
electron. Thus for distances less than r0 the energy corresponding to ^ cvea increases
as r decreases. T h e tw o resulting energy curves are shown in F ig. 5-6.
W e im m ediately recognize th at the energy curve fo r a 0ls or ^ even has a m inimum
at r 0, corresponding to the equilibrium separation o f the tw o protons, which makes
a stable configuration for H f possible. B ut the energy curve for a uls or ψ,,,ια has no
m inim um; thus no stable configuration (o r m olecule) results. T h erefo re w e may
say that t/vven is a bonding wave fu n ction , w h ile f/0dd is an antibonding wave fun ction .
Antibonding w a v e functions and states are designated b y an asterisk and thus we
write a i l s . T h e equilibrium proton separation for the ion in the bonding
a 0ls state is 1.06 X IO-10 m, and the energy o f this state at the m inim um is
— 2.648 e V rela tive to the system H (ground state) + H + at infinite separation. A t
the same separation the energy o f the antibonding a i l s state is about + 1 0 .2 eV
relative to the same reference state.
T h e states o f the H t m olecule w e have discussed correspond to the case in which
the hydrogen atom was in itia lly in its ground state. B ut there are other curves
similar to those o f Fig. 5-6 which correspond to excited electronic states o f the
188 Molecules (5.2

F ig. 5-7. Electron potential energies in H j for the ground state and some excited
states.

m olecule and are associated w ith a hydrogen atom in itia lly in an excited state.
Figu re 5-7 shows a few o f the possible poten tial energy curves corresponding to
excited electronic states o f H j . W e shall explain the designation o f the states
later on.

E X A M P L E 5.1. Discussion of the charge-exchange collision H -f- H + —> I f + + H.

S o lu tio n : Suppose that a beam of fast protons, or H + ions, passes through hydrogen gas
in the atomic state (for which the temperature must be at least 2400°K and the pressure
5.2) The hydrogen molecule ion 189

R eciproca l v e lo c ity , units o f 10 s In -1 s

Fig. 5-8. Electron capture probability in charge-exchange collisions as a function of

the reciprocal of the velocity of the incident proton.

10 microns of mercury or less). The scattered protons are observed at a fixed angle. In
the process of scattering, some of the incoming protons capture the electron from the
hydrogen atoms. It has been found that the probability of electron capture by the in­
coming protons varies with the energy of the protons, showing pronounced maxima at
certain proton energies. Figure 5-8 shows the data obtained by Lockwood and Everhart,
in which the probability of electron capture is plotted against the reciprocal of the proton
velocity. The maximum probabilities occur at the energies shown. The interesting feature
is that the maxima are equally spaced in terms of 1/ti.
The quantum-mechanical explanation is very simple. Initially, when the proton is
very far from the hydrogen atom, the wave function of the electron is very similar to <pi
in Fig. 5-4. That is,

Ψ(1 = 0) = « £ ( ^ c vcn + '/'odd)·

As the proton approaches the hydrogen atom, the wave function becomes time-dependent.
According to Eq. (2.29), the time-dependent wave function may be written as

m = § (& v e „ e _,E</* + <l/adie~'B Ι,Λ)

= + Φαα < Γ <ί' Β' % - ίΕ“ \

where A E = E ' — E is the differenc- ’iB,/,l) e-,i</iStween the <rJ ls and the Ct0Is states of
the proton plus the hydrogen atom system. A t a time I = τ Λ/ΔΕ, we get

t ( t = rfi/A E) = ^OZ-cvcn — i/'od<i)e“ ' K,/# = ^ 2e~’ S‘/A

and the electron has jumped to the incoming proton, since the system corresponds to the
wave function Ψ2 · A t a time t = 2nh/AE, the electron is back about its original proton.
Therefore we may say that while the projectile proton P2 is passing near the target proton
Pi, the electron jumps back and forth from one proton to the other with a period

P = 2rh / A E = li/AE.
190 Molecules (5.2

For electron capture to occur it is necessary that, when the incoming proton p2 leaves the
target proton behind, the electron be near p2. A t the energies shown in Fig. 5-8, the pro­
jectile proton p2 must pass very close (about IO-12 m) to the target proton pi. W e may
assume that the disturbance of the electron wave function occurs only while p2 is within
a section of the path, of length a.
I f the proton's velocity is v, the time during which the interaction takes place is r = a/v.
Suppose that a maximum capture probability occurs at a velocity vi. The time of inter­
action is r i = a/vi. The next maximum capture probability must occur at time

T i = r i + P,

so that the electron has time enough to perform an extra complete oscillation and again
end up close to the projectile proton. Thus P = T i — t j or

Jl = a ( I _ l Y
A K \t>2 vi/

Therefore the difference ( 1/1*2 — 1/ci) between successive maxima must be a constant
value. Experimentally, it is found to have an average value of 6.6 X IO-7 m _ I s. There­
fore we obtain

a A E = ΙΟ" 27 m J ~ 6.3 X IO-9 m eV.

The quantity A E (that is, the energy separation between the σ ίΐβ and the Ct0Is curves)
is not fixed, since it depends on the separation of the protons (see Fig. 5-6). Similarly,
the quantity a is not well defined. Taking an average value of IO eV for A E 1 which is
reasonable according to the curve of Fig. 5-6, we have that a ~ 6 X IO-10 m, or about
six times the molecular diameter, which is also a plausible value.
A more detailed analysis requires atheoretical calculation of the quantity a A E inst
of theestimated values we have given. The agreement with experimental results is fairly
satisfactory.

E X A M P L E 5.2. Calculation of the ground-state energy of H 2 using the wave functions

given by Eq. (5.2).

S o lu tio n : The hamiltonian operator of the moving electron plus the two protons, as­
sumed at rest, is

h2 „2 , e2 / I I , l\ ,c
H = — - — V -j- I --------------- 1
— I 1 (5.3)
2m 4π<ο \ f t Ti rJ

where the first term is the kinetic energy operator of the electron, according to
and the last three terms give the potential energy of the ion, as indicated in Eq. (5.1).
WTien we designate either of the two wave functionsψ„ν<Μ> = Φι + Φ2 and φα,ΐά = Φι — φ ·2
by φ, the average energy of the electron in H 2 , according to Eq. (2.51), is

E = ϊφ'Ηφάτ (54)
ίΦ*Φ dr

L et us assume for simplicity that the two atomic wave functions φ ι and Φ2 correspond to
the same atomic state of energy E a. For example, in the ground state of H j the two are
Is hydrogenlike wave functions. W hen φ ι and Φ2 are real (as they are in the case of Is
5.3) Molecular orbitals of diatomic molecules 191

wave functions), a straightforward calculation, using Eq. (5.4) (which we om it) allows
us to find the average energy of the electron as

E = E° + ^ r ~ f f f <5‘5>

where the positive sign corresponds to ^ rvrn and the negative sign to φ0α · In this equa­
tion S = .ίφ ιφ ·2 dr is called the overlap integral, whose value depends on the extent to
which the atomic orbitals ψι and ^ 2 associated with different protons overlap in space;
that is, the txtent to which φ\ and ψ> have appreciable values over the same region of
space. Obviously S is a function of the separation r of the two protons and increases as
r decreases. Also

A - and B ^ I t l h dr ^ d r.
4irio J Γ2 4π«ο J r\ 4π«ο J ri 4?rto J Ti

The integrals A and R are functions of the nuclear separation, r. A plot of E, given by
Eq. (5.5), as a function of r yields curves similar to those in Fig. 5-6. VVe thus get two
possible energy states, as had been predicted on an intuitive basis, with φίν η correspond­
ing to the lower energy.
In Eq. (5.5) the first term gives the energy of the atom formed by one proton and the
electron and the second term gives the repulsive energy of the two protons. Also A is the
attractive energy of the electron and the other proton, and I i and S are pure quantal
terms that do not have a classical analog. N ote that R is appreciable only if φ i and φο
substantially overlap. I f the overlapping of and φ ·2 is negligible, both R and S are very
small and the energy is E = E a -f c2/4ir«or — A , which when plotted as a function of r
does not show a minimum. Hence it is the overlapping, combined with the symmetry of
the wave function, which gives rise to a stable molecule.

It.,‘I M o lv e u la r O rb ita ls o f MHatomie M o le e u le s

A fte r the I I J molecule, which has on ly one electron, the next-sim plest m olecule is
one which has on ly Hvo electrons, such as H 2. T h e analysis o f this m olecule is
v e ry sim ilar to th at o f the molecule, but w ith som e im portant differences. A s
soon as w c have m ore than one electron, w e must in voke the exclusion principle,
which, as m ay be recalled from the atom ic case (Section 4.3), requires th at we take
into account the spin o f the electrons as w ell as their orbital m otion.
L e t us start b y first discussing the orbital m otion o f the electrons. In a diatom ic
molecule (as well as in any linear m olecule) the electrons do not m ove in a central
field o f force and therefore the angular m om entum L o f an electron does not remain
constant during the m otion. L e t us designate the line passing through the tw o
nuclei as the Z-axis (F ig . 5 -9 ); the resultant force on an electron alw ays passes
through the Z-axis. In other words, the force is axial. In this case the torque on
the electron rela tive to O is perpendicular to the Z-axis and therefore the com ­
ponent o f the angular m om entum o f the electron parallel to the Z-axis, L t , is
constant. T h is com ponent o f th e angular m om entum , as w e know, m ay have the
values L z = mih, where wq = 0 , ± 1 , ± 2 , . . . T h e sign o f m; determ ines the
sense o f rotation o f the electron about the Z-axis; however, the energy o f the elec­
192 Molecules (.5.3

tron is independent o f the sense o f rotation. T h erefore, in order to specify the state
o f an electron, one need g iv e on ly the absolute valu e o f mi (th a t is, λ = |mj|).
T h e differen t angular m om entum states are designated according to the follow ing
scheme:
mi'. 0 ± I ±2 ±3 . ..
λ: 0 I 2 3 . ..
S ym b o l: σ π δ φ . ..

Thus, except for σ -stat.es, all other angu­

lar m om entum states are doubly degen­
erate because o f the double sign o f mj. In
addition, in each o f the ab ove states the
electron m ay have its spin up or down
relative to the m olecular axis (correspond­
in g to m , = +£ and — §, resp ectively)
so σ angular m om entum states can ac­
com m odate tw o electrons, one w ith spin
up and another w ith spin down, and the (a)
rem aining states it , δ, φ, . . . can accom ­ F ig. 5-9. Electronic orbital angular
m odate up to four electrons each, tw o momentum in a diatomic molecule.
w ith spin up and tw o w ith spin down.
F o r m olecular orbital states o f the electron we shall use the notation Xnl (th a t is,
σ η ί, im l, δηΐ, etc.), where n l serves to indicate the atom ic orbitals from which
each o f the m olecular orbitals has been form ed b y linear com bination. E ach of
these m olecular orbital states corresponds to a d ifferent energy.
In the case o f m olecules composed o f tw o identical nuclei, such as I I 2" and H 2.
called homonuclear molecules, there is an im portant sym m etry to be considered.
T hese m olecules have a center o f sym m etry 0 ; the p ro b ab ility distribution o f an
electron must be the same a t points sym m etrically located rela tiv e to 0 . T h erefo re
the w a v e function o f the electron must be the same a t sym m etrical points or must
have the same valu e but opposite signs. T h is is, for exam ple, the situation w e found
for H 2-, corresponding to w a v e functions ^ cvcn and ψ0άά, illustrated in F ig. 5-4.
A n gu lar m om entum states described b y w a v e functions o f the ty p e ψ,.ν,:η are called
3-states and those described b y w a ve functions o f the ty p e 4>,m are called «-sta tes
(fro m the G erm an gerade. or even, and ungerade, or o d d ). Thus for homonuclear
m olecules w e have states <r0, <r„, ir„, iru, etc. T h is explains the n otation w e intro­
duced in Section 5.2.
T o understand how tw o atom s bond to form a m olecule, it is essential to know
the space variation o f the electron p rob ab ility distribution corresponding to each
electron angular m om entum state. T h is has been done for the ffffls and f f j l s states
o f I I 2' in F ig. 5 -5 (b ). T h e procedure to be follow ed in general is the same as in the
case o f H 2". W e start b y considering the tw o atom s separated a v e r y great distance
and guess how the atom ic w a v e functions <pt and ψ2 com bine linearly to form a
m olecular icave fu n ctio n or orbital ψ, as the tw o atom s g et v e ry close.
F igu re 5-10 illustrates a few m olecular w ave functions or orbitals resulting from
linear com binations o f some specific atom ic w a ve functions (o r atom ic orbitals).
 Molecular orbitals of diatomic molecules 193

(a ) Molecular orbitals resulting from s atomic orbitals

(b ) Molecular orbitals resulting from p, atomic orbitaLs

(c) Molecular orbitals resulting from px or py atomic orbitals

g. 5-10. M olecu lar orb itals in hom onuclcar d iatom ic molecules.

194 Molecules

Separated atoms Molecule

2s-
F ig. 5-11. Electronic energy levels
in homonuelear diatomic molecules.

I n this figure o n ly th e angular distribution o f the w a v e functions is shown. F ig ­

ure 5 -1 0 (a ) shows the case in w hich we com bine tw o s atom ic w a ve functions which
are spherically sym m etric. T h e tw o resulting m olecular w a v e functions obtained
b y com bining ψ, and ψ·> in the form s ± ψ2 are shown to the righ t; these cor­
respond to the σ α and σ „ states already discussed for H 2-. In F ig. 5 -1 0 (b ) we have
the tw o m olecular w a v e functions which result from com bining tw o p* atom ic w ave
functions, and in Fig. ό- l 0 (c ) those which result from com bining p x or p„ atom ic
w a ve functions. A ll these functions are m odulated by the radial part o f the w ave
function. Thus, for exam ple, σ α functions resulting from Is, 2s, etc., atom ic or­
bitals have the same angular distribution but d iffer in their radial variation.
T h ose m olecular orbitals which have a nodal plane (indicated b y a dashed line)
perpendicular to the line join in g the tw o nuclei are antibonding, and the others
are bonding. T h e sequence o f the d ifferent energy levels for a m olecule are shown
schem atically in F ig. 5-11. T h e actual separation and ordering o f the energy
levels m ay v a ry from m olecule to molecule, and fo r each m olecule th ey depend
on the internuclear distance.

.*./ K lv e tro n ie Con figu ra tion o f Som e D ia to m ie M olveuleH

L e t us now an alyze som e sim ple diatom ic homonuelear molecules. W e h ave already
discussed the sim plest one, H f , in Section 5.2; w e know th at its ground state con­
sists o f one electron in the σ,,ΐβ state. N e x t w e con­
sider the H 2 m olecule, com posed of tw o electrons
and tw o protons (F ig . 5-12). T h is m olecule is still txZ . - ''''/ ' (
sim ple enough so th a t it is possible to analyze it in / ' J
great detail w ith ou t actually solvin g the Schro- J \ s r'2
d inger equation. T h e total electrical potential V Ir2
energy o f th e system is / X ^ i
rI

E k - - - sJ
p 4X f 0 \ r, r{ r2 r'2 r l2 ' r) Pi r p2

(5.6) F ig. 5-12. The H 2 molecule.

5A) Eledronic configuration of some diatomic molecules 195

T h e first tw o term s correspond to the interaction o f electron Ci w ith protons P 1

and p 2, the third and fourth to the interaction o f e 2 w ith p t and p 2, the fifth to the
repulsion between the tw o electrons, and the last to the repulsion between the tw o
protons. N o te th at because o f the id e n tity o f the tw o electrons w e can no longer
say th at electron Cl belongs to proton P 1 and electron e2 to proton p 2. T h e atoms,
in a sense, have lost th eir in d ivid u ality and instead we h a ve a new e n tity : a
molecule.
T h e next step would be to set up the Sehrodinger equation corresponding to the
above poten tial energy, proceeding as w e did for the H 2" m olecule in Section 5.2.
H ow ever, w e shall not pursue this m ethod; rather w e shall tak e ad van tage o f the
discussion in the preceding section. W e m ay thus consider th at, according to the
exclusion principle, the tw o electrons can be accom m odated in the bonding level
σ,,ΐβ w ith opposite spins, g ivin g the configuration IallI s )2. B oth electrons are in a
bonding state and g iv e rise to a stable molecule. T h e m olecular energy o f this
configuration as a function o f the internuclear distance is given in Fig. 5-13. The
equilibrium separation o f the nuclei is 0.74 X IO-10 m and the energy o f dissocia­
tion into tw o hydrogen atom s in th eir ground states is 4.476 eV . I f the tw o elec­
trons have the same spin, one electron must be in the bonding state σ,,Ι-s and the
other in the antibonding state, cr*I .s, resulting in the configuration (<r„ls)(criIs).
T h e antibonding effect dom inates the bonding effect, and no stable configuration
results, as shown in the corresponding curve o f F ig. 5-13, which has no minimum.

E, cV

N e x t w e m ay consider H e 2", which has three electrons. T w o electrons are ac­

com m odated in the bonding state σ,,ΐβ and the third in the antibonding state
σ ίΐβ , so th at the configuration is (f f „ ls )2( f f il s ) . T h e result is a stable molecule
w ith a dissociation energy equal to 2.5 eV. T h e molecule HJ" also has three elec­
trons, but because the nuclear charge is rela tiv ely small, its dissociation energy is
also v e ry small and its lifetim e is v e ry short. H ow ever, it has been observed
spectroscopically.
196 Molecules (5.4

T A B L E 5-1 E lectronic C o n figu ratio n o f H o m o n u c le a r D ia to m ic M olecules

Dissociation Bond Ground

Molecule Configuration
energy, eV length, A state

OgIs O* 18 ag2s o "2s T u2p <7„2p TT*2p σΰ2ρ

H2 □ 2.05 1.00 2V

H2
0 4.48 0.74 —9

H e2
0 □ 3.1 1.08 a2 „

H e2
0 0 N o t stable ‘2,

Hi2
0 0 0 1.03 2.67 —o

Be2
0 0 0 0 N o t stable ‘ 2*

B2
0 0 0 0 UD 3.6 1.59 3S

C2
0 0 0 0 [Tm] 3.0 1.31 Iv

N2
0 0 0 0 m 0 7.37 1.09 IV
***

O2
0 0 0 0 HUD0 0 ] 5.08 1.21 Jv

F2
0 0 0 0 HE 0 011 2.8 1.44 Iv
—a

N e2
0 0 0 0 [Tm] 0 [mil 0 N o t stable Iv
~8

T h e H c 2 m olecule lias four electrons, tw o in the bonding state CrtfIs and tw o in

the antibonding state f f j l s ; th a t is, (σ „ 1 «)2( σ ί I s )2. T h e result is th at no stable
configuration is produced. T h is explains w h y helium is a m onatom ic gas. H ow ­
ever, an excited I I e 2 m olecule m a y be form ed if one o f the f f j l s electrons is excited
to the bonding state <r„2s, resulting in (er„ls) 2 σ ί Is <r02s.
T a b le 5-1 shows the electronic configuration o f the homonuclear d iatom ic m ole­
cules up to N e 2. T h e table also indicates the binding energy and the bond length
o f th e ground state o f these molecules. Som e interesting features can be seen in
this table. In general, m olecular binding results when tw o electrons w ith opposite
spins concentrate in the region between the tw o com bining atom s; th at is, they
occupy bon din g m olecular orbitals. This, how ever, is not a strict rule, since H e J
has o n ly th ree electrons, and in B 2 and O 2, the last pair o f electrons are in π -
5.4) Electronic configuration of some diatomic molecules 197

orbitals and their spins are parallel instead o f opposed. T h is characteristic o f B 2

and O 2 is due to the fact th at 7r-orbitals can accom m odate up to four electrons,
tw o w ith spin up and tw o w ith spin down, while these molecules have on ly tw o
electrons in th at energy level. From the atom ic case (Section 4.3), w e recall th at
the repulsion am ong the electrons favors the m ost an tisym m etric space w a ve func­
tion. T h is requires the m ost sym m etric spin w a ve function according to the exclu­
sion principle, which means in this case th at the tw o electrons have their spins
parallel. Since the resultant spin o f O 2 is one, the oxygen m olecule has a perm anent
m agnetic dipole m om ent, th ereby explaining w h y oxygen is a param agnetic gas,
while most homonuclear d iatom ic gases are diam agnetic. W e m ay also expect th at
the stab ility o f the m olecule w ill depend on the rela tive number o f bonding and
antibonding pairs o f electrons. F o r exam ple, w e have indicated th at I I e 2 has the
same number o f bonding and antibonding pairs o f electrons and is not stable. T h e
same happens to B e 2; th erefore both m olecules are unstable. On the other hand,
the stab ility o f .N 2, O 2, F 2, and N e 2 (as measured by the dissociation energy)
decreases because the difference between bonding and antibonding pairs for these
molecules is 3, 2 , I, and 0, respectively.
T h e com ponent o f the to ta l orbital angular m om entum o f the electron along the
m olecular axis is given by M /fi, w ith M i = Y iim n - T h e energy o f a given state
depends on the value o f Λ = \Mi\. D epending on whether Λ = 0, I, 2, 3, . . . , the
state is designated by the sym bols 2, Π, Δ, Φ, etc. Cxiven th at S is the resultant
spin o f the electrons in the molecule, the sym bol o f a state or term is 2-s + 1λ . T h e
ground-state terms o f the m olecules in T a b le 5-1 are shown in the last column.
W hen the tw o nuclei com posing a m olecule are different, such as in the case o f
H C l1 C O , and N a C l, the m olecule is called heleronuclear. In these m olecules the
coulomb interaction o f each nucleus w ith the electrons is different, and the m olecule
no longer has a center o f sym m etry. Thus, although the electronic states are still
called or, jt, S, . . . , etc., th ey are not classified as g and u. In general, as we indi­
cated at the beginning o f the chapter, on ly the electrons in the last unfilled shell in
each atom are considered when one is discussing these molecules.
L e t us take, as an exam ple, the case o f N a C l. T h e problem consists in describing
the m otion o f the 11 electrons from the sodium atom and the 17 electrons from the
chlorine atom in the electric field produced b y the nuclei o f N a and C l at their
equilibrium separation (in the gas phase) o f about 2.51 X IO-10 m. T o sim plify
the problem , let us assume that, since the electrons in closed shells are tig h tly
bound to their respective nuclei, they are not affected b y the presence o f a second
nucleus. Also, in line w ith our preceding discussion, those electrons which arc in
unfilled shells and which have their spins coupled are not expected to p articipate
strongly in the binding o f the molecule. Thus w e are left w ith on ly tw o unpaired
electrons, the 3s-electron in N a and one 3p-electron in Cl.
A p p lyin g the same logic as for homonuclear molecules, w e could say th at a stable
structure is produced when the tw o electrons are concentrated in the space between
the tw o atoms. H o w ever, since the nuclear charges are different, the electronic
distribution is n o t sym m etric. In the case o f the N a C l m olecule, the electronic
charge is displaced tow ard the C l nucleus, since the C l nucleus produces a stronger
198 Molecules

a ttra ctive field. T h is results in a m olecule which has an uneven charge distribution
and which is therefore polarized. T h e electric dipole m om ent o f N a C l in the gaseous
phase is about 3.0 X IO-29 m C. I f the 3s-electron o f N a w ere com pletely trans­
ferred to the C l, the m olecule w ould be a dipole o f charge e = 1.6 X IO-19 C and
length equal to the equilibrium separation 2.51 X IO -10 in, thus having a dipole
m om ent equal to 4.0 X IO-29 m C. W e conclude th erefore th at about 7 5 % o f the
electronic distribution o f the valence electron in N a is displaced toward the Cl
atom and w e m ay consider the m olecule as being composed o f tw o ions held to­
gether b y their coulomb attraction. W e m ay express this situation by w ritin g
N a + C l- . T h is ty p e o f m olecular binding is called an io n ic bond, w h ile the situa­
tion described earlier for hom onuelear molecules, w ith a sym m etric electron dis­
tribution, is called a covalent bond.

Ii, eV

r, in

F ig. 5-11. P o tc n tia le n e r g y c u rv e s fo r N a C la n d N a +Cl .

F igure 5-14 shows the potential energy o f the sodium -chlorine system (in the
gas phase) as a function o f the internuclear separation. A t great distances, the
tw o interacting system s arc th e N a and C l atoms and th eir interaction is very
small, so that, the poten tial energy is p ractically constant. A t a separation of
about 12.5 X IO -10 m, the charge transfer from N a to Cl begins to enter into
effect. A s the separation is further reduced, the interaction potential energy re­
sembles the a ttractive coulom b poten tial between the ions N a + and C l- . B u t at
ve ry small internuclear distance the repulsion between the nuclei and the closed
shells o f the tw o ions increases, offsettin g the ionic attraction between N a + and
C l- . T h e m inim um o f the poten tial en ergy or equilibrium position corresponds to
a separation o f 2.51 X IO -10 m.
 Electronic configuration of some diatomic molecules 199

T A B L E 5-2 D issociation E nergies D, B on d L e n gth s ro, a n d Electric D ipole M o ­

m en ts p o f S om e D iato m ic M o lecu les*

Covalent Ionic

Molecule D, eV ro, A P. D Molecule I), eV ro, A P ,D

H2 4.48 0.74 0 NaCl 3.58 2.51 8.5

L i2 1.03 2.67 0 HCl 4.43 1.27 1.07
O2 5.08 1.21 0 LiH 2.5 1.60 5.88
N2 7.37 1.09 0 KBr 3.96 2.94 1.29
C l2 2.47 1.90 0 KF 5.9 2.55 8.60
HI 3.06 1.61 0.38 CsCl 3.76 3.06 9.97
CO 11.11 1.13 0.12 KCl 4.92 2.79 8.0
NO 5.3 1.15 0.15 KI 3.0 3.23 9.24

* The molecules are grouped according to the dominant character of the bond. Electric
dipole moments are expressed in debyes (D ). One D is 3.3 X IO-30 m C.

T h e m olecular orb ital or w a v e function o f a hcteronuclear d iatom ic m olecule

cannot be o f the ty p e g iven b y E q. (5.2), which treats the tw o nuclei in a sym ­
m etric w ay. H ence (if A and B designate the tw o nuclei) instead o f w ritin g Eq. (5.2)
for a bonding m olecular orb it, w e m ust w rite

Φ = φ .\ + λ '/'/ί,

where Φa and f n are the atom ic w a ve functions o f the electron in relation to each
nucleus. T h e param eter λ is chosen so th at the calculated energy agrees w ith the
experim ental value. D epen ding on th e valu e o f λ, the electronic distribution is
enhanced in the region betw een the tw o nuclei or tow ard either o f the nuclei. In
the first case the bond is p redom inantly covalent and in the second case it is m ostly
ionic. F o r m ost hcteronuclear d iatom ic molecules, the situation is interm ediate
between th e pure covalent bond and the pure ionic bond. In general, th e m ore
ionic the bond is, the larger the electric dipole m om ent o f the molecule. F o r ex­
ample, in th e C O molecule, in which both nuclei have sim ilar charges, th e ionic
character o f the bond is less noticeable than the covalent one. T h is is m ade eviden t
by the rela tiv ely small electric dipole m om ent, 0.10 X IO-3 0 m C, o f the molecule.
T a b le 5 -2 gives the dissociat ion energies, bond lengths, and electric dipole m om ents
o f some diatom ic molecules, and also indicates the dom inant character o f the bonds.

E X A M P L E 5.3. Discussion of the Morse potential.

S o l u t i o n : An empirical expression which gives, with some accuracy, the potential energy
of a bound state of a diatomic molecule for a given electronic configuration is the Morse
potential,

E p(T) = DU - (5.7)

where the constants D, a, and ro are adjustable parameters characteristic of each molecule.
200 Molecules (5.4

The graph of E p{r) is shown in Fig. 5-15.

The minimum of E p is obtained by finding
d E p/dr and equating it to zero. Thus

—2Z)ae-a<r-ro>[l - = 0,

which requires that = I or r = ro,

indicating that ro is the equilibrium separa­
tion. A t the minimum the, value of E p is
zero. For very large r the exponential is neg­
ligible and E p tends to the constant value D.
Thus we could say that D is the energy re­
quired to separate or dissociate the molecule
if it is initially in the state of minimum
potential energy. This matter, however, has
to be considered more carefully because of
the so-called zero-point vibrational energy p ig 5_ i 5 M orse potential.
(see Section 5.8).
For small r, E p tends to the value Z>(1 — ear° )2 instead of to infinity, and this is a
limitation of the Morse potential. T o obtain the meaning of the constant a we must
wait until we discuss molecular vibrations (Example 5.7).

E X A M P L E 5.4. Determination of the possible terms of the ground state of some of

the molecules in Table 5-1.

S o lu tio n : When a molecular orbital Xnl has its complete quota of electrons compatible
with the exclusion principle, the only possible state is M l = 0 and S = 0 or state 1IS.
Molecules I I 2, Ilea, Lia1 Be2, Ca, and Fa, in Table 5-1, have their uppermost molecular
orbitals filled and their ground state is 1S. I f only one electron exists in the uppermost
molecular orbital Xnl, obviously Λ = λ and .S = i . This is the situation for IlJ and H e 2 ,
which have λ = 0, and the ground-state term is 2S . Different possible terms occur when
a molecular orbital is not completely filled but has more than one electron, as in B2 and
O2, both of which have the configuration (ir2p)2. The molecular orbital ir2p is made out
of atomic wave functions with mi = ± 1 . Also m, = ± £ . Thus the possible arrange­
ments of quantum numbers (or atomic orbitals) compatible with the exclusion principle
arc given in the following table, in which the symbols correspond to the wave function
(mi, m ,)2.

—I 0 + 1

+2 ( 1, + ) ( 1, - )

+ 1

0 ( I , — ) ( — !, - ) (I , + ) ( — I, - )
(I , + ) ( — !, + )
(I , - K - I , + )

- I

-2 ( - ! , + ) ( — 1, - )
5/i) Electronic configuration of some diatomic molecules 201

From this table we see that we have enough wave functions to make the following molec­
ular states:

Ml = ± 2, M s = 0: 'Δ -state
M l = 0, M s = ± 1 ,0 : 3S-State
M l = 0, M s = 0: 'S-state

Thus there are three possible terms corresponding to the configuration (π2ρ)2, of which
the ground state is that of higher multiplicity, 3S. This is the ground state of Bo and O 2.

E X A M P L E 5.5. Discussion of the potential energy of a diatomic molecule for the case
of ionic binding.

S o lu tio n : An empirical expression which gives a fairly accurate description of the poten­
tial energy for ionic binding is

e2 b
E pIr) = - - ------ + - · (5.8)
drrtor rJ

The first term is the pure coulomb attraction between the ions and the second term ac­
counts for the repulsion of nuclei and closed shells. The exponent 9 was chosen because
it produces the best fit to experimental data by an inverse r" function. Because the
second term depends 011 r -9 , it falls off very rapidly with the nuclear separation and is
important only at small distances. The equilibrium separation r is obtained by finding
the minimum of E„. Thus

e2 96
\ dr / r_ ro , 2 10
4tceof0 r0

giving 6 = c2ro/367r«o. The corresponding energy E p at the minimum, designated D il

is D j = — (8/9)e 2/47reoto· This is the dissociation energy of the molecule. I t is equal to
the energy required to dissociate the molecule, initially in its ground state, into two ions
at rest and separated an infinite distance. In the case of X a C l1 I), gives the energy re­
quired to separate the molecule into the ions X a + and C l- . The energy of the system
formed by X a + and C l- at infinite separation corresponds to the dashed line in Fig. 5-14.
Setting ro = 2.51 X IO-10 m, we find a dissociation energy for X aC l of 5.12 cV. How­
ever, we are interested in the energy required to dissociate X aC l into neutral atoms, such
as X aan d Cl. An energy equal to 5.14 eV is required to ionize a X a atom, while when the
ion C l- is formed an energy equal to 3.72 eV is released. Therefore, the system formed
by X a + and C l- at infinite separation has an energy in excess of the system X a and Cl
at infinite separation, equal to 5.14 eV — 3.72 eV = 1.42 eV.. This means that the dis­
sociation energy D n of X aC l when it is separated into neutral atoms is

D n = 5.12 eV - 1.42 eV = 3.70 eV,

which is somewhat larger than the experimental value of 3.58 eV. One can obtain a better
fit to experimental data if the repulsive inverse r term is replaced by an exponential term
having the form 6 exp ( —r/ro).
202 Molecules (5.5

5 .5 P o Iy a io m U - M o le c u le s
F o r m olecules w ith m ore than tw o atoms, an im portant new elem ent enters into
the analysis o f electronic m o tio n : the geom etrical arrangem ent o f the electrons and
the nuclei (o r in other words, the m olecular s ym m etry ). W e must rem em ber from
the diatom ic case th at bonding is favored when the bonding electrons can fit
w ith in the region join ing tw o atoms. T h is requires th at the atom ic w a v e functions
w hich pertain to the tw o atoms and which m ake up the m olecular orbital extend
or “o v e r la p ” as much as possible along the line join in g the tw o nuclei, favorin g the
condition in w hich a pair o f electrons (one from each atom ) are concentrated be­
tween the tw o atoms. W e m ay state this requirem ent o f “m axim um ov e rla p p in g ”
o f atom ic w a ve functions as follow s:

A bond between two atoms occurs in the direction in which the respective
atomic wave fun ction s m aking up the molecular orbital are concentrated
or overlap; the strength o f the bond depetids on the degree o f overlapping
o f the atomic wave functions.

T h e principle o f m axim um overlap is v e ry helpful when w e wish to determ ine

the shape or geo m etry o f a molecule. L e t us take the case o f the w a ter molecule,
H 2O, for exam ple: it contains 10 electrons and three nuclei. In the oxygen atom
we m ay again forget (in a first approxim ation) all electrons except the tw o unpaired
p-eleetrons in the L-shell (F ig . 4 -3 ). These tw o electrons, which have parallel
spins, as shown in Fig. 4-3, m ust differ in their orb ital m otion. R em em bering
F ig. 3-11, which shows the angular distribution o f the p-electrons, w e m ay assume
th a t one electron is concentrated along the X -axis and the other electron along the
F-axis; th at is, the unpaired 2p-electrons occupy states p x and p,,. (T h e rem aining
2p-electrons o f O are along the F-axi.s, or p x state, w ith th eir spins paired.) T h e
tw o LI atoms, each w ith one Is electron, are located so th at their respective elec­
trons couple in the best possible w ay (th a t is, w ith m axim um overlap pin g o f their
w a v e functions) w ith the tw o unpaired electrons in 0 . T h erefo re w e conclude that,
for m axim um overlappin g to occur, the tw o LI atom s m ust be located on the X -
and F -axe.s, resp ectively, a t equal distances from the 0 atom . T h is results in a
m olecule w ith a right-angle shape, as shown in Fig. 5-16.
N o te th a t in Fig. 5-16 the distribution o f the p-electrons from O is not drawn
exactly equal to that, shown in F ig. 3-11. T h e reason for this is th at the presence
o f the H atom s deform s, or polarizes, the m otion o f the p-electrons from O some­
what. Also the angle between the tw o O — I I bonds is sligh tly larger than 90°
(a c tu a lly it is 104.5°) because o f the repulsion betw een the tw o H atoms. A de­
tailed calculation shows th at the hydrogen ls-electrons are pulled tow ard the O
atom so th at the centers o f mass o f the n egative and p ositive charges do not coin­
cide, producing a polarized m olecule w ith a resultant electric dipole m om ent o f
6.2 X IO-30 m C, along the line bisecting the bond angle. O bviou sly, if the L I2O
m olecule w ere linear, the dipole m om ent would be zero.
N e x t let us consider the am m onia or N I I 3 molecule. T h e three unpaired 2p-
eleetrons in the N atom (see F ig. 4 -7 ) are concentrated along the X -, F-, and Z -
5.5) Polyatomic molecules 203

axes, occupying px, p„, and px states, so th a t the N H 3 m olecule has a p yram idal
structure, w ith the N atom a t one v e rte x and the H atom s a t the other vertexes
form in g the base (F ig . 5 -1 7 ). T h e angles at the N ve rte x o f the pyram id are 107.3°
instead o f 90° because o f the repulsion between the H atoms. T h e pyram id al struc­
ture gives rise to an electric dipole m om ent o f 5.0 X IO-3 0 m C directed along
the axis o f the pyram id. T h e dipole m om ent would be zero if the m olecule w ere
planar.
T h e carbon atom is interesting. In its ground state it has on ly tw o unpaired
2p-electrons, and this cannot explain m any compounds o f carbon. One o f the first
excited states o f carbon, as shown in Figs. 4 -8 and 4-10, consists o f one 2s and
three unpaired 2p-electrons, w ith their orbitals arranged as in Fig. 5 -1 8 (a ). T h e
2p-electrons would act sim ilarly to those o f am monia, but the 2s-electron (because

(a) s, px, |>j, and p. wave functions (b) sp3 hybridized wave functions

F ig. 5-18. W a v e functions resulting from sp3 hybridization.

204 Molecules (5.5

F ig. 5-19. Localized sp3 molecular orbital bonds in (a) methane, (b ) ethane.

o f its lack o f d irectio n a lity ) w ould not produce a bond o f the same strength, m ak­
ing it difficult to explain m olecules such as m ethane, C H 4. I t is possible how ever,
b y means o f the technique called hybridization o f wave functions, to produce new
atom ic w a v e functions oriented in the desired directions. T h e one 2s and the three
2p w a v e functions o f carbon do not h a ve exa ctly the same energy, but the differ­
ence in their energy is v e ry small. B y m aking proper linear com binations o f the
four functions, w e m ay obtain new or h ybrid w a ve functions, all corresponding to
the same energy and having a pronounced m axim um in any desired direction. A
possible set o f linear com binations o f the s, p*, p„, and P 1 functions g iv e four new
hybrid w a ve functions w ith m axim a w hich p oin t tow ard the vertexes o f a tetra­
hedron, as shown in F ig. 5 -1 8 (b ). T h e directions along which the new w a v e func­
tions h a ve their m axim a form angles o f 109°28'. T h e y are expressed in terms o f
the s and p w a v e functions as

Ψι = i(s + Pi + P v + Pz),
= £ (S + P i — p„ - P z ), , .

1^3 = $ (S ~ P x H- P » - P z ),

φ4 = £(s — P i - P „ + P z ).

T h is ty p e o f h ybridization is designated b y sp3. N o te th at because s and p w a ve

functions correspond to d ifferent values o f the angular m om entum , the hybrid
w a ve functions do n ot describe states o f w ell-defined angular m omentum.
N o w let us consider the m ethane m olecule: C H 4. W e conclude th at the m axi­
mum strength o f the bonds is obtained when the Is-electrons o f each hydrogen
atom achieve m axim um overlap pin g w ith each o f the four sp3 h ybrid w a v e func­
tions o f carbon. T h is results in the tetrahedral m olecule shown in F ig. 5 -1 9 (a ).
5.5) Polyatomic molecules 205

}’

X X
(a ) sp2 h yb rid ized w a ve functions ( b ) ρ ζ w a ve function

F ig. 5-20. W ave functions resulting from sp2 hybridization.

Sim ilarly, th e ethane (o r H 3C — C H 3) m olecule has the structure indicated in

Fig. 5 -1 9 (b ). In this m olecule the tw o carbon atoms are held togeth er b y the o v e r­
lapping o f tw o hybrid sp3 w a v e functions. T h is is called a σ -bond, due to its sim ­
ila rity to the situation o f σ -orbitals in d iatom ic molecules.
I t is im portant to recognize th at hyb rid ization applies not on ly to carbon but
to any atom or ion w hich has the same electronic configuration. F o r exam ple, the
ion N + has the same electronic arrangem ent as carbon and the structure o f the
radical N + H 4 is similar to th at o f C H 4, w ith N + replacing the carbon atom.
Besides sp3 hybridization, there are several other possibilities o f h ybridization
including w a v e functions whose angular m om enta h ave values higher than one.
W e shall discuss on ly sp2 and sp hyb rid ization because o f th eir im portance. In
sp2 hyb rid ization the s, p*, and p„ w a ve functions com bine to produce three w a v e
functions in the X T -p la n e , w ith th eir m axim a pointing in directions m aking angles
o f 120°, as indicated in F ig. 5-20. These w a ve functions are expressed in term s o f
the s and p w a v e functions as

(5.10)

T h e fourth electron occupies a p., state. T h is is the typ e o f hyb rid ization re­
quired to explain molecules such as ethylene H 2C = C H 2, shown in Fig. 5-21.
T h e double bond between the carbon atom s results from the overlap pin g o f one
206 Molecules (5.5

(b)

F ig . 5-21. E lectronic distribution in ethylene using sp2 h yb ridization : (a ) σ-bond,

(b ) 7r-bond.

sp 2 hybrid w a v e function from each carbon atom along the line C — C (th a t is, a
σ -bon d) and the overlappin g o f p2 w a v e functions, which constitute a -π-bond, so
called because o f its sim ilarity to the case o f 7r-orbitals in d iatom ic molecules.
T h e hydrogen atoms are attached to the rem aining sp2 hybrid w a v e functions. A s
a result, the ethylene m olecule is planar. T h e double σττ-bond has a certain rigid ity
which m akes it difficult to tw ist the m olecule around the C — C axis. T h is rig id ity
does not occur when there is a single bond, such as there is in ethane, and it has
som e effect on the m olecular properties. N o te th at the degree o f overlap pin g in a
π-bond is m uch less than in a σ -bond, and therefore π-bonds contribute less to the
binding energy than σ -bonds. F o r example, 6.33 e V are required to break a single
σ -bond, but on ly 3.98 e V are needed to break a double σ π -bond into a single
σ -bond.
5.5) Polyatomic molecules 207

s+p.-

F ig. 5-22. W ave functions resulting from sp hybridization.

F ig. 5-23. Electronic distribu­

tion in acetylene using sp hybrid­
ization. (a) W ave functions with
atoms separated; (b ) a- and
7r-bonds.

T h e third ty p e o f h yb rid iza tion w ith s and p atom ic orbitals is called sp, and
corresponds to w a v e functions s ± p „ w hich have pronounced m axim a in the
± Z -d ire ctio n s . These h yb rid w a v e functions are shown in F ig. 5-22. H y b rid sp
w a ve functions are required to explain m olecules such as acetylene, H C = C H
(F ig. 5-23). T h e trip le bond betw een the tw o carbon atom s results from the over­
lapping o f one sp h y b rid w a v e function from each carbon atom (th a t is, a σ -bon d)
and the overlap pin g o f p* and p y w a v e functions, resulting in tw o 7r-bonds. The
hydrogen atom s are attached to the rem aining sp w a ve functions. A s a result,
acetylene is a linear molecule.
208 Molecules (.5.6

F ig . 5-24. Electronic distribution in butadiene, (a) Localized σ-bonds; (b) unlocalized

π-bonds.

ii.G C on ju g a ted M o le c u le »
L e t us now consider a class o f compounds, called conjugated b y organic chemists,
o f which butadiene (C 4H 6) is an exam ple. T h e electronic structure o f butadiene
is indicated in Fig. 5-24. T h e carbon atom s along the chain are bonded b y σ -bonds
using sp2 hybrid w a ve functions. T h e hydrogen atom s are attached to the carbon
atom s using the rem aining sp2 w a v e functions. B u t in addition there are four p2
electrons form ing 7r-bonds along the carbon atom chain. In conjugated molecules
the π -bonds behave in a special w ay. T h e π -bonding electrons— one fo r each
carbon atom — instead o f being localized in particular regions o f the m olecule, as
are the electrons in σ -bonds, are m ore or less free to m ove along the m olecule, as
indicated in Fig. 5 -2 4 (b ) by their prob ab ility distribution. T h e π -electrons accord-
5.6) Conjugated molecules 209

1 2 3 4

F ig. 5-25. Molecular orbitals for ir-electrons in butadiene.

ingly act in a v e ry special w a y which requires further consideration. F o r example,

the p olarizab ility o f the conjugated molecules in the direction o f the carbon chain
is much greater than the p o larizab ility o f saturated hydrocarbons which h ave on ly
localized σ -bonds and sp3 w a v e functions. A ls o the τ -electrons introduce a certain
rigid ity into the m olecular structure, so that all carbon atom s lie in a plane.
L e t us now discuss the w a v e functions or m olecular orbitals o f the four π-
electrons. A t the b ottom o f Fig. 5-25, w e have schem atically indicated the radial
w ave function o f each π-bonding electron when the carbon atom s are all v e ry
distant from one another. W h en the atoms are v e r y close together, as th ey are in
a molecule, the possible w a v e functions are obtained b y m aking proper linear
com binations o f the individual or atom ic w a v e functions. T h e technique is the
same as th at used for and H 2, but now w e have four atom s instead o f two.
Because o f the sym m etry o f the m olecule the m olecular orbitals m ust be either
sym m etric or an tisym m etric rela tive to the center o f the molecule. T h e four pos­
sible m olecular w a ve functions o f the π -electrons are designated b y ψι, ψ2, ψ3ι and
in F ig. 5-25, and each corresponds to a differen t energy, which increases w ith
the number o f nodes o f the w a v e function. T h erefore, as the carbon atoms are
drawn closer, the energy o f the system splits into four closely spaced levels instead
210 Molecules (5.6

F ig. .>-26. Electronic potential energy of ir-electrons in butadiene as a function of

internuclear separation.

o f tw o, as in and H 2. T h e four energy curves are shown q u a lita tiv e ly in

F ig. 5-26, as functions o f the internuclear distance. E ach energy' level can accept
tw o electrons w ith opposite spins. Thus, in the ground state o f butadiene, the
four ττ-electrons occupy the states corresponding to φ ι and φ 2. T h e next tw o nearby
states, corresponding to φ3 and φΛ, are em p ty. T h e resulting p rob ab ility distribu­
tion o f the electron is shown in F ig. 5-27. M olecu lar orbital φ\ is o f the bonding
ty p e for each pair o f carbon atoms, while φ 2 *s bonding for the pairs 1-2 and 3-4
o f carbon atom s and antibonding for the pair 2-3. F o r th at reason th e total prob­
a b ility distribution shows a dip a t the center o f the molecule. T h is means th at the
strength o f the bond between the pair 2-3 o f carbon atom s must be less than for
the pairs 1-2 and 3-4. E xp erim en ta lly th e length o f the bond 2-3 is 1.46 X IO- 10m,
w h ile bonds 1-2 and 3 -4 have a length o f 1.35 X IO-10 m.
Our discussion can easily be generalized to include a polyene or conjugate com ­
pound consisting o f a carbon chain o f 2 n atom s; in the classical valence m odel
this would be w ritten as: · C = C — C = C — C = · · · In addition to the σ -bonds
betw een pairs o f adjacent carbon atoms, there are 2>i 7r-electrons spread along the
molecule, as previou sly shown for butadiene in F ig. 5-24. T h ere are then 2 n
closely spaced energy levels available, w ith cap acity for 4n electrons, to be filled
b y the 2n ir-electrons. H ence when these m olecules are in the ground state on ly
the low er h a lf o f the en ergy levels are occupied. E lectronic m otion in these m ole­
cules can be excited b y a rela tiv ely small am ount o f energy because o f the nearby
em p ty levels. W hen there are 4n 7r-electrons, all energy levels are occupied and,

Ci C2 C3 C-i

F ig. 5-27. Total probability distribution of τ -electrons in butadiene.

5.6) Conjugated molecules 211

F ig. 5-28. Benzene molecular orbitals, (a) Localized σ-bonds; (b ) unlocalized 7r-bonds.

in order to excite the electronic m otion, the m olecule m ust undergo a transition to
another electronic configuration; this requires much m ore energy. T h e avail­
ab ility o f low -lyin g e m p ty energy levels is responsible for the fact th at m any o f
these conjugate molecules absorb photons in the visible region and therefore have
characteristic colors.
As a last exam ple, w e shall consider the cyclic conjugate m olecule benzene,
C e H 6. T h e carbon atom s are located at th e vertexes o f a regular hexagon and
joined b y σ -bonds using sp2 hybrid w ave functions along each C — C line, as shown
in F ig. 5 -2 8 (a ). T h e hydrogen atom s are attached at the rem aining sp2 orbital o f
each carbon atom . T h e re are also six 7r-electrons, one from each carbon atom, in
2/2 Molecules (5.7

p , orbitals (th e Z-axis is taken perpendicular to the plane o f the m olecule). These
7T-electrons are free to m ove along the hexagon, constituting a sort o f closed cur­
rent, as indicated in F ig. 5 -2 8 (b ). T h is accounts for the strong diam agnetism o f
benzene and other cyclic con jugate molecules. T h e analysis o f the w a ve functions
and the energy levels o f the 7r-electrons is sim ilar to th at for butadiene, but the
fact th at the carbon chain is closed introduces som e new features w ith respect to
open carbon chains, which w e shall not discuss (see P ro b lem 6.20).
W e shall not pursue the subject o f m olecular structure any further. T h is b rief
discussion o f chemical binding is enough to illustrate the m ore fundam ental ideas
and to forewarn the student o f the difficulties w hich arise when one attem pts to
use the classical concept o f valen cy in too rigid a form. T h e form ation o f a m ol­
ecule is a m any-particle problem in vo lvin g electrom agnetic interactions, and the
problem m ust be solved according to the rules o f quantum mechanics.

E X A M P L E 0.6. Estimate the first excitation energy of a π-electron in a conjugate

molecule.

S o lu tio n : One can estimate the excitation energy of a π-electron by considering that π-
electrons move independently of each other and that their motion within the molecule
resembles motion in a potential box (Section 2.5) whose dimension is of the order of the
length of the carbon chain. The wave functions would then correspond to the dashed
lines in Fig. 5-25. I f the carbon chain has 2n atoms, there are 2 « π-electrons and the last
occupied electronic level corresponds to the nth level in Eq. (2.14). The energy difference
between the nth and ( n + I) th levels is the first excitation energy. Then

2, 2 , I ,.2 2 ,2 2 2 ,2

Δ£ = Η ^ - - ι ϋ - = ^ (2'ι + 1 ) - (5-n )
where a is the length of the region in which the π-electrons move, taken as the molecular
length extended half a bond length on each end. For example, in the case of butadiene,
with a about 5.6 X IO-10 m and n = 2, we get A E = 5.86 eV, which corresponds to
photons of wavelength 2.12 X IO-7 m. I t has been observed that butadiene has strong
absorption for radiation of wavelength 2.17 X IO-7 m. Thus our crude model shows a
reasonable agreement with the experiment.

.7 .7 X lolvvu ia r R ota tion s

N o w th at we have considered electronic m otion in molecules which have fixed
nuclei, the next step in our analysis o f m olecular structure is to stu d y nuclear m o­
tion. T h e simplest nuclear m otion is th at o f rotation o f the m olecule around its
center o f mass as if the m olecule w ere a rigid body. W e shall first discuss the rota­
tion o f diatom ic molecules.
W e can study the m otion o f a rigid bod y m ost easily b y using a fram e of reference
attached to the bod y and com posed o f the principal axes o f inertia. In the case of
diatom ic molecules (F ig. 5 -2 9 ), the principal axes are the line join ing th e tw o
nuclei, N i and N 2, or the Z 0 axis, and any line perpendicular to it through the
center o f mass. Because their mass is so sm all, w e can neglect the m om ent o f inertia
5.7) Molecular rotations 213

Fig. 5-29. Rotation of a diatomic N1 N2

molecule about its center of mass.
CM,

due to the electrons, and th erefore the m om ent o f inertia o f the m olecule rela tive
to the Z 0 axis is zero. Thus the angular m om entum o f the molecule, for rotation
around the Z 0 axis, is also zero and the to ta l angular m om entum L o f the m olecule
is perpendicular to the m olecular axis. G iven th at r 0 is the equilibrium separation
o f the nuclei and μ the reduced mass o f the m olecule, the m om ent o f inertia about
an axis perpendicular to Z 0 and passing through the center o f mass o f the m olecule
is / = μ τ 0. W e m ay then w rite the kinetic energy o f rotation o f the m olecule as
Er = L 2/21. B y virtu e o f the quantization o f the angular m om entum w e m ay
write, according to E q. (3.15), L 2 = h 2l ( l + I ) , w here Z = 0, 1, 2, 3, . . . , (th a t is,
a positive in teger). T h erefo re the kinetic energy o f rotation o f the molecule becomes

(5.12)
Er = h W + !) = Dhcl{·1 + 1^-

where it is custom ary to set h 2/21 = Jihc. T h e quantities h 2/21 and B for several
molecules are given in T a b le 5-3, expressed in e V and in cm - 1 , respectively. By
givin g successive values to I, w e can obtain the rotational energy levels o f the m ol­
ecule (F ig. 5 -3 0 ). Successive energy levels, corresponding to I and I ' = I + I, are
separated by the amount

AEr = 2 B h c(l + I). (5.13)

T A B L E 5-3 K o tatio n al an d V ib ra tio n a l C o n stan ts o f Som e D iatom ic

M olecules

Molecule h2/2I, eV Ii = h/M rlc cm -1 Λωο, eV v0, cm 1

H2 8.0 X IO- 3 60.809 0.543 4395

C l2 3.1 X ΙΟ" 5 0.244 0.0698 565
N2 2.48 X 10—* 2.010 0.292 2360
CO
CO

O
X

L i2
I

0.673 0.0434 351

O2 1.78 X IO- 4 1.446 0.194 1580
CO 2.38 X 10~4 1.931 0.268 2170
HF 2.48 X IO- 3 20.94 0.510 4138
HCl 1.31 X ΙΟ" 3 10.59 0.369 2990
HBr 1.05 X IO" 3 8.47 0.326 2650
BeF 1.84 X ΙΟ-4 1.488 0.151 1266
2/4 Molecules (.5.7

Parity

F ig. 5-30. Rotational energy states

of a diatomic molecule.

■t

Because o f the sm all valu e o f h 2/ 2 I (~ 1 0 - 4 e V ) when com pared w ith the trans­
lational kinetic energy (w hich is o f the order o f k T ~ eV = 2.5 X IO- 2 e V at
room tem perature), m any molecules are found in excited rotational states at room
tem perature. A lth ou gh the rela tiv e equilibrium population o f th e d ifferent rota­
tional en ergy levels is an im portan t problem , its analysis requires the use o f
statistical m ethods, and w e shall th erefore defer it until Section 12.5. T h e w a ve
functions corresponding to the rotational m otion are the F (m,(0, Φ) introduced in
Section 3.5, and the angles (0, φ) define the direction o f the m olecular axis Z 0 rel­
a tiv e to the coordinate axes X , Y, Z , fixed in the laboratory. H ence the p a rity
o f each le v el is ( — I ) 1, and thus successive energy levels have opposite p arity,
since th ey are sim ilar to the s-, p-, d-, . . . atom ic orbitals. F o r electric dipole
radiation, the allowed transitions are those for which

A f= ±1, (5.14)

a selection rule sim ilar to th at found in the atom ic case. Thus the o n ly transitions
possible are those betw een adjacent levels. Som e o f the transitions, corresponding
to absorption, are indicated in Fig. 5-30. W h en w e use B oh r’s rule, E 2 — E x = hv,
the frequency o f the radiation em itted or absorbed in a rotational transition is

v = A E /h = 2 B c (l + 1 ) or v = 2 B (l + I ) , (5.15)

w here I refers to the angular m om entum o f the low est level in vo lved in the transi­
tions and P is the w a ve number expressed in cm - 1 . Thus th e rotation al spectrum
o f d iatom ic m olecules consists o f a series o f lines equ ally spaced an am ount

A? = 2B cm - 1 .

B y measuring AP, w e can com pute B and thus the m om en t o f inertia, and from it
estim ate the nuclear separation r 0.
Pure rotational spectra fall in the m icrow ave or far-infrared regions o f the spec­
trum . In addition, for a m olecule to exh ibit a pure rotational spectrum , it must
5.8) Molecular vibrations 2/5

v, pm 1

Fig. 5-31. Rotational absorption spectrum of IIC l in the gaseous phase.

possess a perm anent electric d ipole m om ent. In the process o f absorption o f radia­
tion b y the m olecule, the perm anent electric dipole m om ent interacts w ith the
electric field o f the incom ing w ave. In the process o f emission o f radiation, the
rotation o f the dipole is responsible for the radiation. T h erefore, homonuclear
diatomic m olecules (w h ich do not have a perm anent electric d ip ole) d o n ot show
pure rotation spectra. F igu re 5-31 illustrates the absorption rotation spectrum o f
H C l in the gas phase. Each d ip corresponds to a maxim um or resonant, absorption.
W e can see that, in agreem ent w ith the theory, as given b y E q. (5.15), the fre­
quencies are even ly spaced.
Equation (5.12) holds for the case o f a rigid molecule. H o w ev e r, when the
rotational energy increases, there is a stretching o f the m olecule due to a centrif­
ugal effect; this results in an increase in the m om ent o f inertia and a correction to
Eq. (5.12) is required. Our discussion applies also to the rotational spectra of
linear molecules such as COo or IIC N t. T hose m olecules— which, in general, have
relatively larger m om ents o f in ertia— have much closer rotational energy levels
than most diatom ic molecules, and correspondingly low er frequencies in the rota­
tional spectrum.

5./1 M o l w u l a r Vibra tion s

So far w e have considered th e nuclei as fixed rela tiv e to each oth er; how ever, the
shape o f the poten tial energy curve for a diatom ic m olecule (such as those shown
in Figs. 5-6, 5-13, and 5 -14) suggests th a t the nuclei in a m olecule are in rela tive
oscillatory m otion.
L e t us consider a d iatom ic m olecule which has a poten tial energy for a given
electronic configuration, as shown in F ig. 5-32, where r0 is the equilibrium separa­
tion. G iven that the nuclear m otion corresponds to an energy E , the tw o nuclei
oscillate so that, classically, th eir separation varies between Oa and Ob. The
motion o f the nuclei must, how ever, be described according to quantum mechan-
1CS. I f the poten tial energy w ere th at o f a sim ple harm onic oscillator, represented
by the parabola %k(r — r 0) 2, the rela tive oscillatory m otion o f the tw o nuclei
would be sim ple harmonic, and the results o f Section 2.6 w ould be applicable.
216 Molecules · (5.8

T lic angular frequ en cy o f the oscillations is ω 0 = V k /μ, w h ere μ is the reduced

mass o f the molecule. In Section 2.6 it was shown th at the energy o f the oscillatory
m otion is quantized and g iven b y E q. (2.21). H en ce the vib ration a l energy levels
o f a diatom ic m olecule are expressed app roxim ately b y

Ev = ( ο -\- £)Λω0, (δ . 16)

where v = 0, I, 2, 3, . . . (p o s itiv e integer). T h erefo re the vib ration a l energy levels

o f the m olecule are e qu ally spaced an am ount Iicon and th e m olecule has a zero-
p o in l vibrational energy equal to iheo0. Because o f th e zero-poin t energy, the dis­
sociation energy o f a d iatom ic m olecule is D e = D — Ishco0, as m a y be inferred
from F ig. 5-32. T h e selection rule for electric dip ole transitions am ong vibrational
levels is the same as E q. (2 .34 ); th at is,*

Av= ±1. (5.17)

Since the on ly allowed change o f v is to a neighboring energy level, the on ly fre­

quency absorbed or em itted in a v ib ration a l transition is equal to th e natural
classical frequency V0 = ω 0/2ττ. T a b le 5-3 give s the values o f Iieo0 and V0 = V0I c

* This selection rule is not rigorous because the potential energy, as shown in Fig. 5-32,
is not that of a harmonic oscillator, and higher values of Av are also possible, although less
probable.
5.8) Molecular vibrations 217

for several diatom ic molecules. T h e vib ration al frequencies o f m ost d iatom ic

molecules fall in the infrared region o f the spectrum. F o r a v ib ration a l transition
to occur, either in emission or absorption, the d iatom ic m olecule must have a
permanent electric dipole m om ent. T h u s hom onuclear m olecules such as H 2 or
N 2 do not show pure vib ration a l transitions, since they have no perm anent electric
dipole m om ents and they do not exh ibit an infrared spectrum . B ut polar molecules,
such as H C l, show strong vib ration a l transitions.
T h e m olecular energy due to both rotation and vib ra tion can be expressed by
combining Eqs. (5.12) and (5.10), so th at w e have

E = Ev+ Er = ( v + i)ha>0 + ^ j l ( l + I). (5.18)

In general, the qu a n tity Λ2/2/ is much sm aller ( ~ I 0 -4 e V ) than Iicon (~ 1 0 -1 e V ),

and we m ay say that, to each v ib ration a l level, there correspond several rotational
levels, as shown in Fig. 5-33. W h en the selection rules Av = ± I and Al — ± 1
are taken into account for a transition between tw o rotational levels belonging to
two adjacent vib ration a l levels, the rota tion -vib ra tion spectrum results. Th is

V ib ra tio n a l ievels R o ta tio n a l levels

Iii- i ’r= £/<(/+ D V= I

11 I

'-II

-
—2

M ■■ M = +1

Il =0
i

t
hho)o /'-branch //-branch
Δ/ = — I M = + 1

Fig. 5-33. Vibrational and rotational F ig. 5-3-1. Vibration-rotation transitions

energy levels of a diatomic molecule. in a diatomic molecule.
 218 Molecules (5.1
transmission
Percent

W a v e num ber, cm

F ig. 5-35. Vibration-rotation absorption spectrum of HCl. Tlic major dips arc due
to I i 35Cl and the smaller dips are due to H 37Cl.

consists o f lines whose frequencies arc given by

V v.r = r0 ± 2B c (l - f I )
or
IV r = V0 ± 2 B (I + I ) , I= 0,1,2,..., (5.19)

where I refers to th e low er rotational level and B is as defined in Section 5.7. T h e

frequencies are eq u a lly spaced an amount 2Be on both sides o f the central frequency
c 0. T h e line o f frequency V0 is m issing from th e spectrum because it requires a
transition w ith A l = 0, w hich is forbidden. F igu re 5-34 illustrates th e possible
rotation al transitions for the vib ration al transitions v = I —» v = 0. T h o se lines
w ith A l = + 1 are called the /2-branch o f the spectrum ; the name P-branch is
used to designate those lines w ith A l = — I. T h e intensities o f the differen t transi­
tions fo r em ission and absorption depend on th e population o f the initial energy
level, w hich in turn depends on the tem perature o f the substance. W e shall con­
sider this subject in Section 12.5.
T h e ro ta tio n -v ib ra tio n spectrum o f H C l is shown in Fig. 5-35. Because both ro
and I depend on the mass o f the m olecule, the spectra o f m olecules h a vin g d if­
ferent isotopes, such as H 35C l and H 37C l, are s ligh tly displaced. T h is is clearly
recognizable in the figure.
5 .i) Molecular vibrations 219

0 — 0 — 0 · '

F ig. 5-36. Normal vibrations of poly-

atomic molecules, (a)| 0 0 2:ω ι = 1337 cm- *,
Ψ
o>2 = 667 cm-1 , o>3 = 2349 c m - 1; (b) H 2O:
ωί = 3657 cm- 1 , ω'2 = 1595 cm - 1 , ωχ —
ω3 3756 cm

(a )

(b)

uur tn eory can De renned m tne lou ow m g w ay. T n e potential energy curve o f
Fig. 5-32 does n ot correspond to th at o f a sim ple harm onic oscillator and the
oscillations are anharmonic. T h is requires additional term s in E q. (5.18) to prop­
erly describe the vib ration a l energy. In addition, due to the shape o f th e potential
energy curve, the equilibrium separation o f the nuclei changes as the vib ration al
energy changes. T h is results in a change o f th e m om ent o f inertia, and hence of
the rotational energy. T h is is a vib ra tio n -ro ta tio n interaction effect. A ll these
corrective terms are usually obtained em pirically b y analyzing the spectrum of
the molecule.
The vib ration al spectra o f p olyatom ic molecules are m ore com plex. These
spectra are analyzed in term s o f the norm al modes o f vib ration o f the molecule,
which are vib ration s in w hich all nuclei v ib ra te w ith constant phase relations. T o
each norm al m ode there corresponds, in general, a d ifferent frequ en cy o f vib ra-
tion. H ow ever, sym m etry m a y m ake som e o f the frequencies equal or degenerate.
Figure 5-36 shows the norm al vib ration s o f tw o sim ple m olecules: Carbon dioxide,
CO2, is a linear m olecule and H 2O is a planar molecule. F o r a frequ en cy to be
active in the vib ration a l or infrared spectrum, the corresponding norm al vib ration
ttlUst induce an oscillating electric d ipole in the molecule. F or exam ple, consider
sym m etric C O 2 molecule, w hich has no perm anent electric dip ole mom ent.
Oscillation ω , preserves th e sym m etry o f the m olecule and does n ot induce an
eIectric dipole m om ent; th erefore the vib ration al m ode is spectroscopically inactive.
220 Molecules
C5.8

12,000

11,000
(003)-
>(102)_
(201 y
(300) -
JQ22)=
(
(121V
10,000 (220)“ “ 10284
(041)- -9834

(012) - -9000 .
(Ill)-
(210)“ “ 8762
(031)- -8374
(130)“ "8274

( 002)·
( 200) - 7445 (101)- -7251
( 021) 6871
( 120) = =6775

(0 U )_ _5331
(U O )- = 5235

(030)-

(100)- (001)-
3657
( 020) -

(010)-

M ixc d m odes

F ig. 5-37. Vibrational levels of HaO in the gaseous phase. The energies are expressed
in cm -1 . The numbers in parentheses correspond to the vibrational mode (niri2» 3)·

On the other hand, ω 3 induces a dipole m om ent parallel to the axis o f the m olecule
and Co2 a dipole m om ent perpendicular to the axis o f the m olecule; therefore both
are a c tiv e spectroscopically. In cid en tally, co2 is doubly degenerate, since it consists
o f the m ode shown plus one in which the atom s oscillate perpendicular to the page.
A p olyato m ic m olecule therefore has several sets o f vibration al energy levels.
Som e are illustrated in F ig. 5-37 for H 2O. Each o f these levels is associated w ith
corresponding rotational levels, th ereby m aking the spectra rather complex. An
analysis o f rotation -vib ration spectra provides valu able inform ation about m olec­
ular dimensions, geom etry, dissociation energy, and so on.
A n interesting process, called the Ram an e je c t— after the In d ian physicist
C. V . R am an (1888- ) — is related to m olecular vib ration s and rotations, al-
5.8) Molecular vibrations 221

1η term ed in te
o r virtu a l state

- In it ia l
state

^scattered —v rscaltorcd ~ v Cr esrattrird = V-Hel-

R a y le ig li Stokes A nti-S tokes
scatterin g
Ram an scatterin g

F ig. 5-38. Rayleigh and Raman scattering.

thougli it is essentially a scattering process. Suppose that w e illum inate a gas

sample w ith m onochrom atic radiation o f frequ en cy v. I f w e observe the radiation
scattered in a direction at right angles to th at o f incidence, w e find th at the radia­
tion contains, in addition to the frequ en cy v equal to th at o f the prim ary or incident
radiation, which is the coherent or Rayleigh scattering, radiation o f frequ en cy v ± vv
(where vv corresponds to a frequ en cy o f the vib ration al spectrum o f the m olecule).
Th is is called Raman scattering. W e can interpret Ram an scattering in the follow in g
manner: suppose th at a m olecule is in itia lly in the v ib ration a l state v (F ig . 5-38).
When the m olecule absorbs radiation o f frequency v, it m ay go to an excited state.
I f the excited state is not a station ary one, there is an im m ediate re-radiation o f the
absorbed energy. T h e m olecule m ay return to the initial state, em ittin g radiation
of the same frequ en cy as the incident lig h t; this is R a y le ig h scattering. T h e m ol­
ecule m ay also return to another vib ration al level which, due to the selection rule
Av = ± 1 , must be one im m ed iately ab ove or b elow the initial le v e l; this is Ram an
scattering. Thus the em itted radiation has a frequ en cy v + vD or v — vv. The
line o f frequency v — vv is called the Stokes lin e and th at o f frequency v -j- νΏ the
anti-Stokes line. T h e R am an effect has also been observed in the rotational spec­
trum. In this case the selection rule is A l = 0, ± 2 .

E X A M P L E 5.7. Relation between the constants in the Morse potential (Example 5.3)
and the vibrational frequency of a diatomic molecule.

S o lu tio n : Given that E p = D [ I — β-α<Γ_Γο’]2, we may use the expression

= I - x+ W - £x3 -I ,

and retain only the first three terms, an approximation which is valid when x is small.
Setting x — a ir — ro), we have that

E p = I)\a{r — r0) — $a2(r — r0) 2 -I f

= ■Da2Ir - r0) 2 - Da3(r - r0) 3 d (5.20)

222 Molecules (5.9

If the oscillations were harmonic we should have E p - %k(r — ro)2. Thus the first term
in Eq. (5.20) is the harmonic potential energy, and we may write Jfc = Da2. Since
ωο = v fc μ, we then have

ο2 = μωο/2 0 ,

which gives the constant a in terms of known molecular constants. The second term is
the anharmonic potential energy and contributes additional terms to the vibrational
energy, as given by Eq. (5.16). For example, it can be shown that, to the first order, the
vibrational energy can be written in the form

E . = ( a + 4)Λω o — (a + J) 2x Jio>o

where x , = Λωο, 4 D.

.7. U E iv e ir o n ir T r n n M iiio n s in M o Ie e u ie H

A given m olecule m ay have several electronic configurations or stationary states.

L e t us consider, for sim plicity, a d iatom ic m olecule; to each electronic state there
corresponds a potential energy sim ilar to the electronic states o f I I 2*" shown in
Fig. 5-7. T h e tw o nuclei in the excited electronic states L iv e , in general, equ ilib­
rium distances which are different from the one for the ground state. T w o such
poten tial energy curves arc shown in F ig. 5-39. T h e separation o f these energy
curves is o f the order o f I to 10 cV. Thus when a m olecule experiences an elec­
tron ic transition, ju m ping from one electronic configuration to another, the radia­
tion in vo lved falls in the visible or the u ltraviolet regions o f the spectrum.

F ig. 5-39. Vibrational and rotational energy levels associated with two electronic states.
5.9) Electronic Iransilions in molecules '223

T o a given electronic state there correspond m any vib ration al states and to each
vibrational state there correspond several rotational states. A s a first approxim a­
tion, w e m ay w rite the energy o f the m olecule in the form

E = Ec + E v+ E r = E c + [p + ft)Aw0 + /(/ + I), (5.21)

where E c refers to the electronic energy at the m inimun of the poten tial energy
curve (see Fig. 5-39). In an electronic transition all three energies m ay change.
T h e frequency ω 0 and the m om ent o f inertia I are, in general, differen t for both
electronic states. T h e refo re wc must w rite the energy change in the electronic
transition as

ΔΛ = E" — E' - A E c -i- A E v -t A E r

where A E c = E c — E c is the change in electronic energy, given b y tb c energy d if­

ference o f the m inimum o f the tw o electronic states,

AEv = E" - E 'v = (v " + J)*Wo - (" ' + 4 )M i

is the change in vib rational energy, and

. AEr = EV - Ei = I " (I" + I) - ~ I '(I ' + D

is the change in rotational energy. T h e terms w ith double primes correspond to

the state o f higher electronic energy and those w ith single primes to the state of
lower electronic energy. T h e frequency o f the radiation em itted or absorbed in
an electronic transition is therefore the sum o f three terms,

" = X = ^ T V ) + V rK ", I '),

where vc — A E ,/ h is due to the change in electronic energy, and vv(v " , ν’) and
vr( l " , I ') correspond to the changes in vib ration a l and rotational energies, respec­
tively. T h e frequency vc is the largest. For a given electronic transition the
spectra consist o f a scries o f bands; each band corresponds to a given value o f v "
and ν' and all the possible values o f I " and I'.
T o determ ine the possible values of (υ ", ν ') and ( I " , I ') w e need selection rules.
W hen w e consider electric dipole transitions, the rotational selection rule is

Al = 0, ± 1 , no I " = 0 <-► /'= 0.

N o te that Al = 0 is now allowed because there is a change in configuration of the

molecule during the transition and p arity considerations do not enter in in the
same w ay as in previous cases. H ow ever, the transition I’ = 0 «-» I " = 0 is for­
bidden because, if it were allowed, it would then be im possible to satisfy the prin­
ciple of conservation of angular m omentum, since the radiation em itted or absorbed
carries one unit of angular momentum.
224 Molecules (5.9

An oth er selection rule is that the spin o f the m olecule m ust be the sam e in both
electronic states in vo lved in the transition; th at is, A S = 0. T h is rule is due to
the fact th a t the spin-dependent forces in vo lved in the transition are n ot strong
enough to alter the coupling o f the electrons’ spin; how ever, this selection rule is
n ot rigorously followed.
T h e vibration al selection rule is som ewhat m ore in volved . N o te th at an elec­
tronic transition occurs in a tim e o f the order o f IO-16 s, w h ile th e nuclear oscilla­
to ry m otion has a period o f about IO-13 s, or one thousand tim es longer. T h ere­
fore, during the electronic transition, the nuclear separation rem ains essentially
the same. T h is means th at a line join in g the initial and final positions o f the
nucleus in Fig. 5-39 at the tim e o f the transition must be vertical. On the other
hand, the m ost favorab le transitions must be those for w hich it is easiest to qu ick ly
adjust the nuclear m otion to the new electronic conditions. In term s o f classical
m echanics, the m ost favorab le vibration al transitions should occur when the rela­
tiv e nuclear v e lo c ity is the same in both states at the tim e o f the transition. Since
the nuclear v e lo c ity is zero at the ends o f the classical oscillation, the most probable
transitions occur when, at the time of transition, the nuclei are at one end o f their oscil­
lation and at the same internuclear distance f o r both the in itia l aiul fin a l states. In
the language o f quantum mechanics, w e could say that the m ost probable transi­
tions are those for which the vib ration a l w a ve function suffers th e least distortion
at the tim e o f the transition. Since the oscillatory w a v e functions are v e ry sim ilar
at the classical ends o f oscillation (rem em ber F ig. 2 -1 9 ), w e reach the same con­
clusion w ith the quantum -m echanical m odel as w e do w ith the classical model.
L e t us refer to F ig. 5-40, for exam ple, and suppose that a m olecule in itia lly in
the vibration al state ν' = 5 o f electronic state C ' suffers an absorption transition
up to electronic state C " . T h e most probable final v ib ration a l states are obtained
b y draw ing vertical lines a and 6 at the ends o f the classical oscillation and extend­
ing them up to intersect c u r v e C " . L in e a falls near v " = I, resulting in a transition
v' = 5 —* v " — I. Line b falls ab ove the dissociation energy and would result in
the dissociation o f the molecule. W h en the transition involves the lowest v ib ra ­
tional state ( v' or v " = 0), the v ertical line should be drawn through the center o f
the oscillations, as in c and d, resulting (in our exam ple) in the transition

ν' = 0 - » v" = 4
and
ν' = 2 -> v " = 0.

T h e reason for this is th at the m axim um o f the w a v e function for the ground
state o f an oscillator occurs at the center (see F ig. 2-19). W e have considered
absorption transitions; the same logic applies to emission transitions. T h erefore
vib ration a l transitions associated w ith electronic transitions do not com ply w ith
the selection rule Av = ± I and v m ay suffer a change o f several units.
T h e rule w e have explained for determ ining the vib ration al transition in an
electronic transition is known as the Franck-C oiulon p rin ciple. I t was form ulated
first in classical term s b y James Franck and reform ulated according to quantum
m echanics b y E dw ard U. Condon about 1926.
5.10) Conclusion 225

F ig. 3—40. Electronic transitions allowed by the Franck-Condon principle.

5.10 I onclusion
In our discussion o f m olecular structure w e h ave considered on ly the most im ­
portant aspects. T h e re are m any details th at w e have not m entioned. F o r example,
nuclear spins h ave an influence on m olecular energy levels. In the simplest m ol­
ecules, H f and I I 2, the tw o protons m ay have th eir spins parallel or antiparallel,
resulting in orthohydrogen and parahydrogen.
M olecu lar sym m etry plays a v e ry im portant role in determ ining th e possible
normal vibrations as w ell as the allowed transitions; how ever, a discussion o f
m olecular sym m etry is beyond the level o f this book.
In the case o f polyatom ic molecules the spectra m ay be so com plex th at it m ay
be impossible to classify them as w e have done in Section 5.9 for the spectra of
diatom ic molecules. H o w ev e r, this com p lexity serves a useful purpose, in th at it
perm its us to id en tify a g iven com pound by observing its spectrum. On the other
hand, certain atom ic groups exhibit w ell-defined electronic and vib ration a l spectra.
Observation of the corresponding frequencies serves as an indication of the presence
o f such groups in a molecule.
W e m ay conclude by saying th at one o f the most pow erful tools for determ ining
molecular structure is the analysis o f m olecular spectra.
226 Molecules

RoierpnveH

1. "T h e Force Between Molecules,” B. Derjaguin1Sci. Am., .Iuly 1960, page 47

2. “ Some Aspects of Molecular Physics,” J. Levelt1 .lm. J. I 'In/s. 28, 192 (1960)
3. “ Chemistry of the Noble Gases,” H. Selig, J. M alm .^nd H. Claassen, Sci. .Dn., M ay
1964, page 66
4. “ The Zeeman Effect in Molecules,” C. Quailc, bn. J. Phys. 32, 634 (1964)
5. The Scientific Endeavor. New Y ork: Rockefeller Institute Press, 1965; “ The Architec­
ture of Molecules," by L. Pauling
6. Symmetry in Chemistry, I’ . Dorain. Reading, Mass.: Addison-Wesley, 1965
7. The Structure of Molecules, G. Barrow. New Y ork: Benjamin, 1964
8. Electrons and the Covalent Bond, II. Gray. New Y o r k : Benjamin, 1965
9. Elements of Wave Mechanics, N. M ott. Cambridge, England: Cambridge University
Press, 1962, Chapter 5, Sections 2.3, 3, 4.2, 4.3, 4.4, 4.5, and 4.6
10. Structure of Matter, W . Finkelnburg. New Y o rk : Academic Press, 1964, Chapter 4,
Section 7; Chapter 6
11. Quantum Theory of Matter, J. Slater. New Y ork: M cGraw-Hill, 1951, Chapters 8
and 9
12. Elementary Introduction to Molecular Spectra, B. Bak. N ew Y ork : Interscience, 1960
13. Chemical Binding and Structure, J. Spice. N ew Y ork: Macmillan, 1964
14. Wave Mechanics and Valency, J. Linnett. London: Methuen, 1960
15. The Chemical Bond, third edition, L. Pauling. Ithaca, N .Y .: Cornell University Press,
1967

P r o b Io n iM

5.1 The ground-state energy of H f rela­
tive to the system composed of hydrogen
in its ground state and H + at infinite sep­
aration is — 2.65 eV. Compute: (a) the
energy of I l / relative to the system
H++ H++ e
at infinite separation; (b) the energy of the
system Ho' + e at infinite separation rela­
tive to the system H + H, again at infinite
separation, and with both atoms in their
ground states; (c) the ionization energy of
Ho if the dissociation energy of this mol­
ecule into two hydrogen atoms in their
ground states is 4.48 eV. Compare the
result in (c) with the ionization energy of
atomic hydrogen.
5.2 Calculate the contribution of the
coulomb repulsion of the two nuclei to the
energy of Ho in its ground state. Compute
the energy due to the interaction of the
electron with the nuclei. [H in t: Use the
data of the preceding problem and recall
that the equilibrium separation of nuclei
in H ^ is 1.06 A.]
5.3 Dissociation and ionization energies
are frequently expressed in kcal mole-1 .
Show that one kcal mole-1 is equal to
4.338 X IO-2 eV. Expressthedissociation
energy of H 2 in kcal mole-1 .
5.4 Explain why the bond length of H j is
1.06 A, while H j has a shorter bond length
equal to.0.74 A. Also explain why the dis­
sociation energy of LIj (103.2 kcal mole-1 )

is less than twice the dissociation energy of
(61.06 kcal mole-1 ).
5.5 Explain why the ion H j" is less stable
than the ion H e i if both have the same
electronic configuration. Which ion should
have the laf-ger internudear separation?
5.6 Find the energy of L ij relative to the
I system 2 L i+ + 2 c , with all four particles
at infinite separation. The ionization
energy of lithium is 5.39 eV. Calculate
the coulomb repulsion energy of the Li +
ions at the equilibrium separation, 2.67 A .
Then compute the energy of the two val­
ence electrons.
5.7 Discuss the electronic configuration
and bond structure of (a) A I2, (b) S2, and
(c) CI2. Write, in each case, the symbol for
the ground-state term.
5.8 Given the molecule NO , discuss its
electronic configuration and bond struc­
ture. Compare with the N 2 molecule and
state. Decide which molecule is more
stable.
5.9 Write the electronic configurations for
the following heteronuelear diatomic mol­
ecules: (a) L iH 1 (b) C N 1 (c) SO, (d) C lF 1
and (e) H I. Determine, whether the mol­
ecules arc polar and, in the affirmative case,
identify which end of the molecule is
positive and which end is negative.
5.10 Calculate the energy released when
AlCl and A lIlr dissociate into neutral
atoms. The equilibrium separations for
these molecules are 2.13 A and 2.30 A ,
respectively. The respective experimental
values are 71.5 kcal mole-1 and 55.3 kcal
mole- 1 . [H int: Sec Example 5.5 for a sim­
ilar calculation for NaCl.)
5.11 When a hydrogen atom captures an
electron to become I I - , an energy equal to
0.. 49 eV is released. The ionization energy
of lithium is 5.39 eV. Compute the dis­
sociation energy of LiH , given that the
nuclear equilibrium separation is 1.60 A.
5.12 An acceptable empirical expression
for the potential energy in ionic bonding is
Problems 227
given by
E , = —v2e2/(4 rtur) + be~3-3xlu '° rt
where v is the charge of the ions and b is
a constant determined from experimental
values for the dissociation energy. Find 6
for K C l, given that the equilibrium dis­
tance for this molecule is 2.79 X IO-10 m.
Plot the potential energy. Find the dis­
sociation energy of K C l into K + and C l- .
Calculate the energy required for its dis­
sociation into neutral products.
5.13 A fairly precise empirical expression
for calculating the potential energy of two
ions in an ionic bond is
E , (r ) = — e2e2/(4jre0r) b e ~ " — d/r®,
where v is the charge of the ions and a,
6, and d are constants obtained experi­
mentally. For L iF the constants arc: a =
3.25 A - ’ 1, 6 = 895 eV, and d = 2.68 eV A®.
Determine the energy required to disso­
ciate a L iF molecule into its two ions. (The
bond length of L iF is 1.54 A .) Also com­
pute the energy required for dissociation
into two neutral atoms. The ionization
potential of lithium is 5.39 eV and the
electron affinity of fluorine is 3.45 eV.
5.14 Show that the wave function
i = N ( s + Oip1 + /Spv + Tp1)
has its maximum along the direction of the
vector a = UxO + u j 3 + u,7, and its
minimum in the opposite direction. IIcnce
two hybrid wave functions corresponding
to vectors a and a ' have their maximum in
directions making the same angle as a and
o'. Write the vector a for each of the sp3
and sp2 hybrid wave functions introduced
in Section 5.5. Show that in the sp3 case
the vectors point toward the vertexes of a
tetrahedron, making angles of 109° 28', and
in the sp2 case they are in the XT-plane,
making angles of 120°. [H in t: Note that
the vector uxpx + uvpv + u,p, is propor­
tional to r.]
228 Molecules
5.15 Show that the four sp3 hybrid wave
functions are orthogonal. Repeat for the
sp2 wave functions.
5.16 Discuss the bond structure in
(a) C3H 8, (b) C 3H 0, and (c) C3H j.
5.17 Analyze the bond structure of the
following molecules: (a) C O 2, (b) CS2,
(c) C S T e, (d) Cs, (e) C dC l2l (f) O C l2,
(g) O N C l1 (h) SnCl2, (i) S§-, and
(j) C N 3 - . Indicate which molecules are
linear and which are bent.
5.18 Analyze the bond structure of the
following molecules: (a) AsH 3l (b) SbF3,
(c) I lO i- , (d) 0 H 3+ , (e) P C l3, (f) SeO §-
(g) HrO3", (h) SiF-i, and (i) P F 3. Indicate
which molecules are planar and which are
pyramidal.
5.19 Analyze the bond structure of H II3
and B H i", indicating whether the mol­
ecules are planar or pyramidal.
5.20 Discuss the H 2O and N H 3 mol­
ecules, using sp3-hybridized wave func­
tions for the oxygen and the nitrogen
atoms, respectively. Do you think that
this is a better description of these mol­
ecules than the one presented in the text?
5.21 Analyze the bond structure of C H 3"
and I i 3O +.
5.22 Discuss the bond structure of the
molecule H 2CO. Is the molecule planar?
5.23 The electric dipole moment of H 2O
is 6.2 X IO- 30 m C. Find the dipole mo­
ment corresponding to each O— H bond.
Given that the bond length of O— H is
0.958 A, what fraction of the hydrogen
electron has been transferred to the oxy­
gen atom?
5.24 The effective total length of the con­
jugate molecule C H 3— (C H = C H — JiC H 3
is 9.8 A. Plot the energy levels occupied
by the π-electrons. Find the energy and
wavelength of the photons absorbed when
one of the uppermost π-electrons is excited.
5.25 The /3-carotene molecule is a conju­
gated molecule having 22 π-electrons. It
has been found that this molecule shows
strong absorption of radiation at 4510 A.
Estimate the total length of the molecule.
5.26 Show that the moment of inertia of
a diatomic molecule about an axis perpen­
dicular to the line of nuclei and passing
through the center of mass is I = pro,
where μ is the reduced mass of the mol­
ecule and ro is the internuclear distance.
5.27 The adjacent lines in the pure rota­
tional spectrum of 35C l19F are separated
by a frequency of 1.12 X IO10 Hz. AMiat
is the interatomic distance of this molecule?
5.28 (a) Calculate the energy and wave­
length of the photon absorbed when a
200H g35Cl molecule (ro = 2.23 A ) makes
the rotational transitions I = 0 —» I = I
and I = I —> I = 2. (b) In what region of
the electromagnetic spectrum are these
lines found?
5.29 Suppose that the equilibrium sep­
aration in the H 35Cl and H 37Cl molecules
is the same and equal to 1.27 A. Compute
for each molecule (a) the constant B for
the rotational levels, (b) the energy of the
first two excited rotational leifels, (c) the
frequencies and wavelengths correspond­
ing to the transitions I = 0 —* I = I and
I = I —> I = 2, and (d) the frequency
difference for successive lines. Compare
your results with Fig. 5-31.
5.30 Compute the energy of the first three
excited rotational states in CO and CO2.
Determine the wavelength of the photons
absorbed in transitions among such energy
levels.
5.31 The rotational energy levels of a
molecule having two equal principal mo­
ments of inertia are given by
_ I ,2 , I Λ Λ ,2
rot 2/i + 2 \/2 Z1/ *’
where I i corresponds to axes X and I' and
12 corresponds to the Z-axis, and
L 2 = 1 (1 + I )Λ2, L 1 = Ui h .

Using this equation, estimate the relative
position of the rotational energy levels of
a molecule having (a) 12 = Ο.8 /1, (b) 12 =
1.2/i. Plot the levels as multiples of
h2/2h .
5.32 A diatomic molecule is not rigorously
rigid and, due to a centrifugal effect, the
internuclear distance increases as the angu­
lar momentum of the molecules increases.
(a) IIow should this molecular stretching
affect the energy levels, in comparison
with the values given by Eq. (5.12)?
(b) An empirical expression for the rota­
tional energy is
Ε ,ο ι = { h 2/ 2 1 ) {1(1 + I) - 51/(1+ I)]2},
where b is the stretching constant. Obtain
an expression for the frequencies due to
transitions among rotational levels. Com­
pare with Eq. (5.15) and see if the stretch­
ing effect is recognizable in Fig. 5-31.
m1
F ig. 3-41
5.33 T w o bodies of masses mi and m2,
respectively, are joined by a spring with an
elastic constant k (Fig. 5-41). Show that
if the spring is stretched and released the
masses will oscillate with a frequency
v = ( 1/2jt)V k /μ, where μ is the reduced
mass of the system.
5.34 Calculate the energy of the three
lowest vibrational levels in H F, given that
Problems 229
the force constant is 9.7 X IO2 N m -1 .
Find the wave number of the radiation
absorbed in the transition e = 0 —* e = I.
5.35 The infrared spectrum of CO, at low
resolution, shows an absorption band cen­
tered at 2170 cm -1 . Find the force con­
stant in CO. Plot, to scale, the potential
energy curve.
5.36 Calculate the ratio of the vibra­
tional frequencies of 1I I 35Cl and 2H 35Cl
molecules, assuming that the force con­
stant is the same for both molecules.
5.37 What is the force constant for the
HCl molecule, given that the vibrational
frequency is 9 X IO13 Hz? Also find the
zero-point energy.
5.38 Find the vibrational frequencies of
IID and D 2, given that the Ho molecule
absorbs infrared radiation of wavelength
2.3 X 10-G m corresponding to a vibra­
tional transition with Ac = I and no
change in rotational or electronic energies.
Assume the same force constant for the
three molecules. Compare with the experi­
mental values.
m2
5.39 The three vibrational frequencies of
CO2 are 667.3 cm -1 , 1388.4 cm -1 , and
2349.4 cm -1 . Make a sketch of the first
few vibrational energy levels of this
molecule.
5.40 The molecule CO has an electronic
transition that produces several bands in
the visible region (around 6000 A). Esti­
mate the separation among adjacent
rotational lines in each band. Do you
expect the band to appear continuous in
a low-resolution spectroscope?
 6
SOLIDS

6 .I Introduclion
6.2 Types o f Solids
6.3 Band T
6A Free-Eleelron M odel o f a Solid
6.5 Electron M o tio n in a Period ic Structure
6.6 Conductors, Insulators, and Semiconductors
6.7 Quantum Theory o f Electrical Conductivity
6.8 Radiative Transitions in Solids
6.2) Types of solids 231

S.1 In tro d u c tio n

M a tte r in bulk, in the w ay it affects our senses, is an aggregate o f a v e r y large
number o f atoms. G rossly speaking, these aggregates appear to be in three physical
states or phases: gases, liquids, and solids. In gases the average distance between
molecules is much greater than the size o f the m olecules and the interm olecular
forces are much weaker than the forces which hold the atom s in the m olecule
together. Thus in gases the m olecules retain their ind ivid u ality. A t the other
extreme, in a solid, the atom s (o r m olecules) are tig h tly packed and held in m ore
or less fixed positions by forces, o f electrom agnetic origin, which are o f the same
order o f m agnitude as those in volved in m olecular binding. T h u s the shape and
volum e o f a solid remain essentially constant so long as the physical conditions,
such as pressure and tem perature, do n ot undergo any appreciable change. Liquids
fall in between gases and solids. H o w ever, the th eory o f liquids is still incom plete
and w ill not be considered in this text.
In m ost solids the atom s (o r m olecules) do not exist as isolated entities; rather
their properties are m odified b y the nearby atoms. T h e regular arrangem ent o f
the atom s or groups o f atom s is one o f the m ost im portant features o f solids; that
is, the structure o f solids exhibits a regularity or p eriodicity constituting w hat is
called a crystal lattice; therefore, to understand the structure o f a solid, it is neces­
sary to study on ly the basic unit or cell o f the lattice, since all properties repeat
from cell to cell. One o f the m ost effective m ethods o f analyzing a crystal struc­
ture is b y means o f x-ray or neutron diffraction.
F rom the quantum -m echanical p oin t o f view , determ ining the structure o f a
solid does not differ, fundam entally from determ ining th at o f a molecule. I t con­
sists in finding a'stab le configuration o f nuclei find electrons which are subject to
their electronic interactions and which m ove according to the laws o f quantum
mechanics. T h e tw o main differences between the structure o f a solid and that o f
a m olecule are the large number o f atoms in volved and the regu larity in their
arrangem ent. Several typ es o f approxim ations are used to study the structure o f
a solid, depending on the dom inant factors in volved in each solid. In this chapter
w e shall an alyze som e o f these m ethods and ap p ly t hem in order to explain certain
properties o f solids, leavin g some considerations o f a statistical nature for C hap­
ter 13.

β.2 Typott o f Solidtt

Solids m ay be classified according to the predom inant ty p e o f binding. In this
section w e shall b riefly discuss the m ost representative typ es o f solids.

(I) C o v a le n t, s o lid s . In a covalent solid the atom s are bound togeth er b y local­
ized directional bonds sim ilar to those found in our discussion o f the H 2 molecule.
T h e crystal lattice is determ ined by the orientation and nature o f the directional
bonds. A typ ica l case is diam ond, in which the four bonding electrons o f each
carbon atom are oriented as shown previou sly in F ig. 5-18 b y means o f sp3 hybrid
 232 Solids (6.2

F ig. 6-1. Diamond lattice.

w a v e functions, resulting in the crystal structure indicated in F ig. 6-1. Each ball
represents a carbon nucleus and each bar a pair o f localized bonding electrons.
T h e separation between tw o carbon atoms is 1.54 X IO-10 m.
C ovalen t solids, because o f their rigid electronic structure, exhibit several com ­
m on m acroscopic features. T h e y are extrem ely hard and difficult to deform . AU
arc poor conductors o f heat and electricity because there are no free electrons to
carry energy or charge from one place to another. A lso a rela tiv ely high energy is
required to excite whole-crystal vib ration s in a covalent solid due to the rigid ity
o f the bonds. W h ole-crystal vib ration s therefore have a high frequency. Sim ilarly,
electronic excitation energies o f covalent solids are o f the order o f a few electron
v o lts (fo r exam ple, the first electronic excitation energy o f diam ond is about G eV ).
T h is electronic excitation energy is rela tiv ely large com pared w ith the average
I therm al energy (o f the order o f k T ) , which at room tem perature (298 cK ) is about
2.4 X IO- 2 e V ; hence covalent soljjls are n orm ally in their electronic ground state.
M a n y covalen t solids are transparent, especially diam ond, because their first
electronic state is higher than the photon energies in the visible spectrum, which
lie between 1.8 and 3.1 eV.

(2 ) I o n i c c r y s ta ls . A t the other extrem e are ionic crystals, which consist o f a

regular array o f p ositive and negative ions resulting from the transfer o f one elec-
i tron (o r m ore) from one kind o f atom to another. T h is is, for exam ple, the case
for N a C l and C sC l, whose crystal structures are shown in Fig. 6-2. T h e separation
between the N a and C l atom s is about 2.81 X 10~ 10 m, while the shortest distance
between identical atoms is 3.97 X IO-1 0 m. T h e ions are so arranged th at a stable
configuration is produced under their m utual electronic interactions.
 6.2) Types o} solids 233

(a)

F ig . 6-2. (a) N aC l lattice; (b ) CsCl lattice.

T hese solids, because th ey have no free electrons, are also poor conductors of heat
and electricity. H ow ever, at high tem peratures the ions m ay gain som e m ob ility,
resulting in better electrical con du ctivity. Io n ic crystals are usually hard, b rittle,
and have a high m elting point due to the rela tiv ely strong electrostatic forces be­
tween the ions. Som e ionic crystals stron gly absorb electrom agnetic radiation in
the far infrared region o f the spectrum. T h is p rop erty is associated w ith the energy
needed for exciting lattice vibrations. T h is energy is gen erally low er for ionic than
for covalent crystals, due to their rela tiv ely weaker binding force. F igu re 6-3
shows the transniission o f infrared radiation through a thin (1.7 X IO- 7 m ) sodium 7
chloride film ; m axim um absorption occurs at a w avelen gth o f 6.11 X IO- 5 m or a '
frequency of 4.91 X IO 12 H z, corresponding to photons w ith an energy of
2.03 X I t r 2eV.

Fig. 6-3. Transmission of infrared

radiation through a N aC l film.
[Adapted from R. Barnes, Z . Physik
73, 723 (1932)]

λ, IO-

L
234 Solids (6.2

H 11 H
F ig . 6-4. Electronic configura­
tions of L i + and F - . N K H
Lr

M o s t ionic crystals are diam agnetic because the ions, having a com plete shell
structure w ith all electrons paired, have no net m agnetic m om ent. F o r exam ple,
in L iF , the ions L i + and F - have the configurations shown in F ig. 6-4, w hich
resemble, resp ectively, the configurations o f the inert gases H e and N e (rem em ber
F ig. 4 -7 ). T h is sim ilarity is also reflected in another im portant p rop erty. T h e
ions are spherically sym m etric, and thus their binding does not show directional
preference, as do those o f covalent solids. T h e refo re the ions are arranged in the
crystal as if th ey w ere closely packed spheres. T h e re are an infinite number o f
w ays o f packing spheres. T w o com m on ones are shown in F ig. 6 -5 : the cubic-
close-packed (ccp ) and the hexagonal-close-packed (hep ).

F ig . 6-5. (a) Cubic close-packing (ccp) of spheres;

(b) exploded view of ccp; (c) hexagonal close-packing
(hep) of spheres; (d) exploded view of hep. (d)
6.2) Types of solids 235

(3) H y d r o g e n - b o n d s o lid s . C losely related to ionic crystals are the hydrogen-

bond solids, w hich are characterized b y stron gly polar molecules havin g one or
m ore hyd rogen atoms, such as w ater, H 2O, and hydrofluoric acid, H F . T h e posi­
tiv e hydrogen ions, since th ey are rela tiv ely small, m ay attract the n egative end
o f other molecules, form in g chains such as

(H + F - ) (H + F - ) (H + F - ) . . .

Th is is p articularly interesting in the case o f ice, in which the w ater m olecules have
the tetrahedral arrangem ent shown in Fig. 6- 6. T h e rela tiv ely open structure o f
ice accounts fo r the larger volu m e which ice has b y com parison w ith w ater in the
liquid phase.

(4 ) M o le c u la r s o lid s . These solids are m ade o f substances whose m olecules are

not polar. A ll electrons in these molecules are paired, so th at no covalen t bonds
between atom s o f tw o differen t molecules m ay be formed. M olecules in this typ e
o f solid retain their ind ivid u ality. T h e y are bound b y the same interm olecular
forces that exist between m olecules in a gas or a liquid: van der Waals forces, which
are v e ry weak, and which correspond roughly to the forces between tw o electric
dipoles. T h is m ay be explained as follow s: Although, on the average, these m ole­
cules do not have a perm anent electric dipole m om ent, their electronic configura­
tion at each instant m ay g iv e rise to an instantaneous electric dipole. T h e van der
W aals forces result from the interaction o f these instantaneous electric dipoles.
F or the ab ove reasons m olecular solids are not conductors o f heat and electricity,
have a v e ry low m elting point, and are v e ry com pressible and deform able. E xam ­
ples o f m olecular solids are C H 4, C l2, I 2, C O 2, C eH e, etc., in their solid state.
In e rt gases, whose outer shells are
com plete, solid ify as m olecular sol­
ids. F igu re 6-7 shows the potential
energy curves describing the inter­
action between tw o atom s o f an inert
gas in the solid state.

F ig. 6- 6. Arrangement of water

molecules in ice. [From L. Pauling,
The Nature of the Chemical Bond.
Ithaca, N . Y . : Cornell University Press,
1960; Iiy permission of the publisher.]
236 Solids (l6.2

F ig. 6-7. Van der Waals interatomic potential energy for inert gases.

(5 ) M e t a ls . F in ally, there are the metals, which are solids o f great practical and
theoretical im portance. M eta ls are elements which have rela tiv ely small ionization
energies, and whose atom s have on ly a few w eak ly bound electrons in their outer­
m ost incom plete shells. These outerm ost w eak ly bound electrons are easily set
free using the energy released when the crystal is form ed. A m etal thus has a regu­
lar lattice o f spherically sym m etric positive ions th at rem ain when the outer­
most electrons are set free. T hroughout this structure there is an electronic “g a s "
form ed b y the released electrons which are responsible for the bonding. These
electrons m ove, m ore or less freely, through the crystal lattice and th erefore are
not localized.
M e ta llic solids exhibit excellent therm al and electrical con du ctivity, for which
the free electrons are m ainly responsible, the reason being th at the free electrons
easily absorb any energy from electrom agnetic radiation or lattice vib ration s— no
m atter how sm all— and thus increase their kinetic energy and their m ob ility. F o r
this same reason m etals are also opaque, since the free electrons can absorb the
photons in the visible region and be excited to one o f the m any elose-b’y quantum
states availab le to them. T h e free electrons are also largely responsible for an­
other characteristic exhibited by m etals: their high reflection coefficient for elec­
trom agnetic waves, especially in the radio-frequency and infrared regions. Forces
holding the m etal lattice togeth er are spherically sym m etric; therefore these lat­
tices resem ble the closely packed spheres discussed for ionic crystals.
T h e preceding classification o f types o f solids should not be taken too s trictly;
som e solids are a m ixture o f m ore than one type. A n interesting exam ple is graphite
6.2) Types of solids 237

F ig. 6-8. Graphite lattice.

(th e graph ite lattice is shown in F ig. 6 -8 ), which consists o f layers o f carbon atoms
arranged in the form o f a hexagon. T h e atom s in a layer are bonded by localized
covalent σ -bonds which use sp2 h ybrid w ave functions and nonlocalized T-bonds,
as in benzene (Section 5.6). T h e nonlocalized rr-bonding electrons are free to m ove
parallel to the layers, which explains the electrical con d u ctivity o f graphite parallel
to the layers but n ot perpendicular to them. Successive layers o f atom s act as
macromolecules. These layers are held togeth er b y weak van der W a als forces, just
as m olecular crystals are, which accounts for the flaky, slippery nature o f graphite.
In fact, it is because o f this structure that graphite is used as a lubricant. T h e
length o f the sp 2 bonds in graphite is I .42 X I O ' 10 m and 'the separation between
thei layers is 3.35 X I 0 -IO m.

O O O O O O O O O O

O O O O O O O O O O
O O O O O O O O O
O O O O O O O O O
O O O O O O O O O
O O O O O O O O O
O O O O O O O O O O

O O O O O O O O O O
O Ό O O O O O O O
(a) (b) O O O O O O O O

O O O O O O O O
O O O O O O O O O O
O O O O O O O O
O O O O O O
° n ° ° n ° O O O O O O O O
O O O O O O O O O O
O O O O O O O O
O O O O O O O O O O
O O O O O O O O
O O O O O O O O O O (e)
(c) (d)

F ig. 6-9. Imperfections in a crystal lattice.

-
238 Solids (6.2

T h e structure o f each o f the types o f solid th at w e have described is determ ined

by the electronic structure o f the com ponent atoms, which indicates the ty p e and
number o f electrons available for bonding, as w ell as the energy required to adjust
their m otion to the conditions prevailin g in the lattice (conditions which are d if­
ferent from those in the isolated atom s). In general, when a solid is form ed, a given
am ount o f energy is required in order to m od ify the m otion o f the electrons; how­
ever, much m ore energy than this is released in the process o f lattice form ation.
C rystal lattices are not perfect, and the im perfections in them m ay be due to
several causes. F igu re 6-9 illustrates som e o f the m ost typ ical im perfections. In
(a ) w e have a vacancy left by a missing atom, w h ile in (b ) w e have a substitutional
im p u rity replacing an atom o f the lattice. Im p erfection s due to an interstitial
atom— either o f the same ty p e or o f an im pu rity— are shown in (c ) and (d ). F in ally
(e ) shows an edge dislocation, w hich m ay be looked upon as if an extra layer o f
atom s had been pushed halfw ay through the top o f the lattice. L a ttic e im perfec­
tions have a m ost im portant effect on m any electric, elastic, and optical properties
o f solids.

E X A M P L E 6.1. Calculation of the internal potential energy of an ionic crystal.

S o lu tio n : Since, in a first approximation, we may consider an ionic crystal as a regular

array of positive and negative point charges, we may expect that the internal potential
energy of an ionic crystal is essentially due to the electric interaction between the ions.
Let us consider, as an example, the case of NaCl, and calculate the electric interaction of
a N a + ion with all other ions in the crystal. As we can see from Fig. 6-2, each N a + has
6 C l- ions as nearest neighbors, all at the same distance. Thus, since both N a + and C l-
have charges which are equal in absolute value to e, the attractive electric potential
energy of N a + due to the 6 nearest C l- ions is

where R is the distance between nearest neighbors. The next series of ions are 12 N a +
ions at a distance s/2 R, resulting in a repulsive potential energy

N ext follows a group of 8 Cl - ions at a distance \Ζ3 R, producing an attractive potential

energy

The next layer contains 6 N a + ions at a distance 2R, producing a repulsive potential
6.2) Types of solids 239

This process continues until all the crystal is included. The resultant potential energy is
their sum or

" ' - - S £ » ( " - ί | + ά - 3+ ) - - ώ · <β 1 >

where a is the value of the sum inside the parentheses, and is called Modelling's constant.
In the case of a face-centered-cubic lattice such as NaCl, the Madelung constant is
a = 1.7476. In general, a depends only on the geometry of the crystal; for a body-
centered lattice, such as CsCl, its value is 1.7627.
Since a is positive, the potential energy is negative and the interionic force is attractive
at all distances, with no minimum. Therefore the crystal should coalesce into a closely
packed structure with no stable configuration. However, we know that this is not the
case. The conclusion results from considering the ions as point charges. When two atoms
come very close together the nuclear repulsion (partially screened by the electron shells)
and the repulsion among the filled electron shells enter into effect. Therefore we must
add a short-range repulsive term to the potential energy. W e did this before, in Sec­
tion 5.4, when we were discussing ionic bonds. T o obtain this repulsive term we assume,
on an empirical basis, a reasonable expression for the potential energy. Several expres­
sions have been proposed, but we shall consider only the simple one suggested by the
German physicist, Max Born (1882- ):

F
K “ 47Γ£οβ ” ’

where β and n are two constants to be determined. When we use R n with n > I, the
repulsion is a short-range force which is negligible at large distances in comparison with
the coulomb ionic attraction. When this potential energy is added to Eq. (6.1), the effec­
tive potential energy is

£’ - - ά ( ΐ - £ ) ' <6·2)

The graph of this potential energy is similar to that illustrated in Fig. 5-14. Calling Ro
the equilibrium separation, we have that, at this distance, dEp/dR — 0. Thus

\ d R J K -K 0 4 π {0 \ R2
0 Rn
0+1J

or β = a R Z -'/ n . Then we may write Eq. (6.2) in the form

ae2 Γ fto I /ΛοΥΙ

" ~ 4jri0f i o L R n \ R j \'

The equilibrium potential energy of the N a + ion, obtained by setting R = Rol is

2
F = ae
Atc o R o ( " = )·
240 Solids 06.2
W e find a similar result if we start with a C l- ion. T o obtain the total internal energy of
the crystal, we must add the above result over all ions in the crystal. When we do this,
we must make sure we do not count the interaction between each pair of ions twice.
Thus, given that N is the number of ion pairs in the crystal (which in our case is the
same as the number of molecules), the internal potential energy of the crystal is

κ - - ϊ £ έ ( ' - 0 · «>

The experimental value of U for N aC l is —7.77 X IO5 J mole-1 or — 185.7 kcal mole-1 .
This result is obtained by measuring the heat of formation of the crystal. Substituting
this value of U in Eq. (6.3), with N equal to Avogadro’s number (6.02 X IO23 mole-1)
and Ro = 2.81 X IO-10 m, we obtain n — 9.4. For other cubic crystals the value of n
is of the same order of magnitude. This value of n is consistent with other calculations.

- Q - O- -O ~ ® T
-n -l ii+ l

F ig. 6—10. Linear lattice of identical atoms.

E X A M P L E 6.2. Discussion of lattice vibrations.

S o lu tio n : The analysis of lattice vibrations is of a great importance because of its bear­
ing on many physical properties of crystals. For simplicity let us consider a linear lat­
tice; that is, a row of identical atoms separated the distance a (Fig. 6-10). The position
of the nth atom is given by x n = na. Let us call ξ„ the displacement of the nth atom
relative to the equilibrium position. As a first approximation we shall assume that during
the vibrations each atom interacts only with its tw o neighbors. The separation between
the nth and (n-f- I ) th atoms has increased by ξ „ + χ — and if β is the elastic constant
of the bond, the force on the nth atom to the right due to the (n + l)th atom is

β (ζ η + ι - ίη).

Similarly the (n — l)th atom produces on the nth atom a force to the left equal to

0 (ί„ - ζη —ΐ).

Thus the equation of motion of the nth atom is

.2 ,
.1/ ~ ~ = β(ξη + 1 - ί„) - β(ξ„ - ί„ - ΐ)

= β (ίη + 1 + ξη-1 ~ 2ξ„). (6.4)

W e shall disregard all end effects, and therefore we try a solution of the form

ϊη = ioei(" l+ *ne). (6.5)

The term kna gives the phase of each atom and resembles the phase term kx in a wave
propagating through a continuous medium. Substituting Eq. (6.5) in Eq. (6.4) and
6.2) Types of solids 2 il

canceling common factors, we get

— Μ ω 2 = /S(e'*“ -f- e ~ 'ka — 2) - —4/3 sin2 \ka,

from which we obtain

ω = 2s/ β/M sin \ka. (6.6)

This equation gives the allowed frequencies in the lattice. N ote that the maximum
value of ω occurs for k = ir/a. The variation of ω as a function of k is shown in Fig. 6-11.

F ig . 6-11. Frequency of lattice vibrations as a function of k.

The fact that there is a maximum frequency means that there is an upper limit or cutoff
frequency for the elastic (i.e., acoustical) waves in a solid. However, this limit, of the order
of IO15 H z for most substances, is well beyond the ultrasonic frequencies so far developed
in the laboratory.

HH

F ig . 6-12. Linear lattice composed of two kinds of atoms.

Let us now consider a lattice composed of two kinds of atoms of masses M i and M 2,
arranged alternately so that the distance between neighboring atoms is 0 and the lattice
space period is 2a (Fig. 6-12). A typical lattice of this type is an ionic crystal. A calcula­
tion similar to that of the previous paragraph shows that the allowed frequencies are
given by
2 o / l / I . I Y 4 sin2 Λ α ] 1,2 . .
" ~ β KJih + W2) ^ β \ΙΓ ι ^ lF i) ~ MiM2 J ' ( )
Now there are two values of ω for each value of k, as illustrated in Fig. 6-13(a). The
upper values of ω constitute the optical branch and the lower ones the acoustical branch
of the frequency spectrum of the lattice. Actually the situation is somewhat more com­
plex than our analysis implies because both the acoustical and optical branches can
242 Solids (6.2

ω ω

(a) (b)

F ig. 6-13. Acoustical and optical vibrations of a linear lattice.

(b ) O p tica l m ode

F ig. 6—I -t. Phase relations among atoms in the acoustical and optical modes.

correspond to longitudinal or transverse (relative to the direction of propagation) vibra­

tions, with two transverse modes corresponding to the two independent directions of
vibration. Therefore, for each value of k there are six possible values of o>(fc), as shown
in Fig. 6—13(b). The reason for naming the branches “acoustical” and “ optical” is that
in the acoustical mode both classes of ions oscillate in phase, while in the optical mode
they have a phase difference of ir. When we consider the transverse vibrations, the
displacements of the ions in the acoustical and optical modes of vibration give the
patterns shown in Fig. 6-14. As we may see from the figure, the induced dipole
moment in the optical mode is much larger than in the acoustical mode, and therefore
6.3) Band theory of solids 243

the optical mode shows stronger emission and absorption of electromagnetic radiation
than the acoustical mode. The optical frequencies fall in the infrared region of the
spectrum, and hence ionic crystals display a strong response to infrared electromagnetic
radiation. For infrared radiation (where the frequency is of the order of IO12 H z and
the wavelength is of the order of IO-4 m), the value of k is of the order of IO4 m _1.
On the other hand, the value of a for most ionic solids is of the order of IO-10 m.
And so ka is about IO-6 , which is a very small value. Hence the resonance frequency
of the crystal for electromagnetic radiation may be obtained by making ka ~ 0 in
Eq. (6.7); that is,

- - K st + s )· <6«

This, for example, is the frequency corresponding to maximum absorption in the absorp­
tion curve for NaCl shown in Fig. 6-3.
In a more refined analysis, the normal modes of vibration of a solid must be quantized.
When we disregard the zero-point vibrational energy of the solid, the vibrational energies
for each mode are multiples of hu{k). Excitation or de-excitation of a vibrational mode
corresponds to absorption or emission of the energy fiu(k). The similarity to the absorp­
tion or emission of radiation suggests introduction of the concept of a phonon, which has
an energy E = hoi(k), a momentum p = hk, and which propagates through the lattice
with a velocity equal to the group velocity V0 = dE/dp = άω/dk. Many thermal proper­
ties of solids, such as heat capacity and heat conduction, can be described in terms of
phonon interactions with the lattice and the transport of phonons through the lattice.
I t is even possible to speak of the scattering of phonons by the atoms <5f the lattice (similar
to the Compton scattering of photons by electrons). This scattering of phonons can be
used to describe the attenuation of high-frequency sound waves through a solid, and the
thermal effects associated with this attenuation.

6 .3 B a n d T h e o ry o f SoUdtt
W hen w e discuss the arrangem ent o f electrons in solids we m ay follow a procedure
v e ry sim ilar to the m olecular orbital technique used in C hapter 5 for analyzing
m olecular structure. W hen an electron m oves past an ion, the poten tial energy it
feels is the coulomb poten tial energy, proportional to I /r, as shown in Fig. 6 -1 5(a ).
I f instead o f one ion w e have tw o ions, as in the H j and H 2 molecules, the poten­
tial energy is like that indicated in Fig. 6 -1 5 (b ). F o r a v e ry large number o f ions

H H

(a ) (b ) (c )

F ig. 6-15. Coulomb potential energy due to (a) a single ion, (b) two ions, (c) several
ions in a row.
244 Solids (6.3

E3

E2

E1

F ig. 6-16. Types of energy levels in a linear crystal lattice.

regularly placed in a row, resem bling a one-dim ensional crystal lattice, the poten­
tial energy appears as in F ig. 6 -1 5 (c ). I f w e neglect the end effects, the potential
energy exhibits the same p eriod icity (o r regu larity) as th e crystal lattice. A n
actual crystal is a three-dim ensional lattice and the poten tial energy o f an elec­
tron m ovin g through the lattice also has a three-dim ensional p eriodicity, repeating
from one cell to the next.
T o determ ine th e possible stationary states o f m otion in such a periodic poten­
tial energy, w e have to return again to the Schrodinger equation. T h e solution
w ill depend on the specific form o f th e periodic p oten tial energy. H o w ever, the
fact th at the poten tial energy is periodic allows us to obtain a certain am ount o f
useful inform ation w ith ou t actually solvin g Schrodinger’s equation. L e t us con­
sider a linear crystal lattice composed o f JV ions separated the distance a (F ig . 6-16).
A n electron havin g an energy such as E i cannot m ov e freely through th e lattice
but is confined m ainly to one o f the classically allow ed regions A B , C D , etc. It
is true th at it can go from A B to C D b y leaking through the poten tial barrier
interposed between the tw o allowed regions (as explained in connection w ith the
inversion o f N H 3, in Section 2.8), but the barrier is rela tively so high and wid e that
its penetration b y the electron is highly im probable. T h is is w h y the innerm ost
electrons in a crystal are essentially localized and th eir energies and w a v e func­
tions, practically speaking, m ay be considered the same as in the isolated atoms.
A n electron w ith energy E 2 is not bound so stron gly to a particular ion and, b y
leaking through the potential barrier, it can m ove about in the lattice. F in a lly an
electron w ith energy E 3 is n o t bound to any atom in particular; it has great free­
dom o f m ovem ent throughout the lattice. These quasi-free electrons are not on ly
responsible for m ost o f the collective properties o f the lattice (such as the electric
and therm al con du ctivities), but th ey also p rovid e for the binding o f the atom ic
ions w hich form the crystal structure.
Our next task is to determ ine the possible energy levels. W e recall the situation
found in H 3" and H 2 molecules. T h e poten tial energy in d iatom ic m olecules is
due to tw o ions and, as a result, the atom ic energy levels sp lit into tw o as th e inter­
ionic distance decreases (F ig . 5 -4 ). S im ilarly, in linear conjugate m olecules having
π -bonding electrons— such as the polyenes (Section 5.6)— the electrons m ov e in
a periodic poten tial energy and each atom ic energy level splits into a number o f
levels equal to the number o f atoms. T h is was illustrated in F ig. 5-26 for butadiene.
6.3) Band theory of solids 245

N
en ergy
curves

F ig . 6-17. Energy levels in n linear crystal

lattice as a function of the interionic
distance.

In terio n ic distance

Therefore, in a lattice such as th at o f F ig. 6-1G, each atom ic energy level gives rise
to N closely spaced levels. T h e ir spacing and position depend on the interionic
separation, as shown q u a lita tiv e ly in F ig. 6-17. F o r exam ple, for an interionic
distance a, the possible energy levels fall between P and Q. W hen N is v e r y large
the different energy levels are so closely spaced th at one m ay say th ey form a
continuous band o f energy.
Since, according to P a u li’s exclusion principle, each level can accom m odate tw o
electrons, one w ith gpin up and the other w ith spin down, an energy band cor­
responding to a given atom ic state can accom m odate a m axim um o f 2N electrons,
or tw o electrons per ion. T h e bands are designated as s-, p-, d-, etc., according to
the valu e o f the angular m om entum o f the atom ic state to w hich th ey are related.
T h ere are m any energy bands in a given crystal lattice, each corresponding to
one o f the energy levels o f the atom s that m ake up the lattice. F igu re 6-18 shows
the energy bands corresponding to several energy levels a t an interionic distance a.

E n erg y In terion ic
bands distance

F ig. 6-18. Energy bands.

246 SolidS (6.4

F rom the energy curves a t the right, w e can see th at the higher the atom ic energy
level, the larger the interionic distance at which the bands begin to be formed.
T h e reason for this is th at the greater the energy o f the electrons, the larger the
region o v e r which they m ove, and therefore the m ore easily they are affected by
nearby ions. A n oth er feature is th at as the interionic distance decreases the bands
begin to overlap. F o r example, for the interionic distance a', the third and fourth
bands in F ig. 6-18 overlap. This, as w e shall see later, is o f great im portance in
explaining the properties o f m any solids.
Bands associated w ith the inner com plete shells in the parent atom s have their
full qu o ta o f electrons allowed b y P au li’s principle. E lectrons in these bands are
also m ore or less localized, as explained in connection w ith F ig. 6-16. T h erefo re
w e shall ignore these bands in our subsequent discussion. H o w ever, the band cor­
responding to the upperm ost atom ic shell, occupied b y the valen ce electrons, is
the m ost interesting in connection w ith the solid p roperties; it is this band th at we
shall consider in m ore detail. I f this upperm ost band is not com pletely filled, it is
called the conduction band. B u t if it is full, it is called the valence band, and the
em p ty band just ab ove it is then called the conduction band.

6. / Frpp -E lpp tron 3I oi I p I o f a Solid

A s a first approxim ation in our analysis o f the m otion o f electrons in the conduc­
tion band, let us ignore the periodic fluctuation o f the potential energy and assume
that th e electrons m ove in a region o f constant average potential energy. H ence
w e m ay consider these electrons as if th ey w ere free and m ovin g independently.
Also, for sim plicity, w e shall consider a linear lattice. I f w e assume th at the lat­
tice is sufficiently large, our discussion w ill not be influenced b y the boundary
conditions at the la ttice ends. H ence the approxim ate w a ve function o f an electron
o f m om entum p = file is

φ = eikz. (6.9)

W e consider th at k can be either positive or n egative to allow for m otion in both

the p ositive and n egative X -dircctions. F o r a three-dim ensional lattice, w e must
have a w ave function which can be described as follow s:

i = ei k r . (6.10)

F o r both w a v e functions, |^|2 = I, which means th at the electron has the same
p ro b ab ility o f being found at any place in the lattice. Th is, o f course, is not in
agreem ent w ith our picture o f the lattice as a periodic structure whose periodicity
should be reflected in the electron’s p ro b ab ility distribution. (F o r exam ple, it
seems reasonable th at there w ould be a greater p ro b ab ility o f finding an electron
near a p ositive ion o f the lattice than in other regions o f the lattice.) H o w ev e r, the
frcc-electron m odel, although crude, does p rovid e som e insight into the properties
o f m any solids.
6.4) Frce-elcctrori model of a solid 247

F ig . 6-19. Energy of a free electron as a

function of fc.

T h e energy o f the electron described b y w a v e function (6.9) or (6.10), if we

disregard the constant average potential energy, is

E — p 2/2m,, = h2k 2/2mv ( 6 . 11)

corresponding to the kinetic energy o f an electron w ith m om entum p = hk. T h e
energy as a function o f k is illustrated in Fig. 6-19. T h e free-electron m odel allows
all values o f k and therefore o f E k, which means th at the m odel does n ot p rovide
inform ation about the w id th o f a band, but we m ay estim ate it in the follow in g w a y :
Consider a linear lattice o f length L composed o f N ions separated the distance a,
so th at L = N a . T o sustain standing waves, the electron’s w avelen gth λ must
satisfy the requirem ent η (λ/ 2 ) - L . F or each value o f n, a given stationary state
results. B u t w e know th at a band in a lattice composed o f N ions has on ly N
states. T h erefo re the possible values o f n are I, 2, 3, . . . , N . N o tin g th a tfc = 2 ιτ/λ,
we then have that

nir/ L = m r/ N a , n = I, 2, 3, . . . , N . ( 6 . 12)

T h e difference between successive values o f fc is ττ/Ν α, which is v e ry small if N is

very large and justifies treating fc as a continuous variab le in spite o f the quan­
tization condition (6.12). S ettin g n = N in E q. (6.12), we find th at the m axim um
value o f fc is
fc,n ax = Ir/a. (6.13)

Thus the range o f fc-values allowed within the band is between — ir/a and ir/a,
as indicated in Fig. 6-19. T h e m axim um energy in the band, which is also the
width o f the band, is then

fl Tl
(6.14)
Emax ~ 2m ea 2

N o te from E q. (6.14) th a t the w id th o f the band is independent o f the number o f

ions com posing the lattice, a result to be expected, since adding m ore ions means
248 Solids

~20kT

(a) Ground state (b) E cited state

F ig. 6-20. Density of energy states of F ig. 6-21. Distribution of free electrons
free electrons in a solid. among energy states in the conduction band.

m ore states; but the p eriodicity o f the lattice, w hich determ ines kmax according to
E q. (6.13), remains the same (see E xam ple 6.6).
I t is m ost im portant to determ ine how the electrons m a y distribute them selves
in a band am ong the energies from zero up to E max. In E xam ple 2.4 w e showed
th at the number o f energy levels in the energy range d E availab le to a free particle
enclosed in a box o f volu m e V is given by

d N (E ) = 4 7rl^ m 3) 1' 2 E 112 dE.

Each level can accom m odate tw o electrons (on e w ith spin up and one w ith spin
d ow n ). T h erefo re, if we refer to one unit o f volum e, the total number o f electrons
per unit volu m e w ith energy between E and E d E in the band is

dn = 87r^ p l' - E m dE = g {E ) dE. (6.15)

A·5

T h e qu a n tity g (E ) = dn/dE is shown in F ig. 6-20, which is basically identical to

F ig. 2-12. F o r a given band the curve should stop at. E max. T h e number o f elec­
trons per unit volu m e that can be accom m odated up to an energy E is g iven by

n = I E g ( E ) dE.
Jo

T herefore, using E q. (6.15), w e get

n = 81r^ p m I E 112 d E = 167r^ p 1/2 E 312. (6.16)

Ei Jo Slij

I f the m etal is in its ground state (which, as w ill be seen later, occurs at absolute
zero), all electrons occupy the low est possible energy levels com patible w ith the
exclusion principle, as indicated in F ig. 6-21 (a ). I f the total number o f electrons
6A) Free-eleclron model of a solid 1U9

T A B L E 6-1 Ferm i Energy

Metal Li Na K Rb Cs Cu Ag Au Mg Al

«f , eV 4.72 3.12 2.14 1.82 1.53 4.07 5.51 5.54 7.3 11.9

per unit volu m e n0 is less than the total number o f energy levels availab le in the
band, the electrons w ill then occupy all energy states up to a m axim um energy,
designated b y ep, and called the F e rm i energy. I f we set E = e? in Eq. (6.16), we
must have n = n 0. T h erefo re for the Ferm i energy w e obtain the value

i F
= JL f^o)2''3. (6.17)
8 me \ TT /

Thus the energy distribution o f electrons in the m etal ground state corresponds to
the shaded area in F ig. 6-20. W h en the F erm i energy is equal to the energy band
width, the band is fu lly occupied. T a b le 6-1 gives the calculated values o f the
Ferm i energies o f a number o f metals.
W hen a band is not com p letely full, a small am ount o f energy is enough to
excite the upperm ost electrons to nearby energy levels, as indicated in Fig. 6-21 (b ).
H ow ever, on ly the upperm ost electrons can be th erm ally excited, since k T at room
tem perature is about 0.025 eV, which is v e ry small com pared w ith ep, and the
exclusion principle makes it im possible for the low -energy electrons to be excited
into nearby occupied states. T h e distribution o f electrons am ong the energy levels
in a therm ally excited state o f the lattice corresponds to the shaded area in F ig. 6-22.
T h e electrons w hich have been th erm ally excited are those w ith an energy greater
than ej.·. T h e states occupied b y the excited electrons fall in an energy region o f the
order o f 20 k T above Cf-

Fig. 6-22. Occupation of energy states at a

temperature different from absolute zero.

T h e work fu n ctio n o f a m etal is the energy w hich is needed to extract an electron

from the highest occupied level. A t absolute zero the F erm i energy is the upper­
most occupied level. Since th erm al energies are v e ry small com pared w ith the
Fermi energy, on ly a v e ry few electrons are excited above the F erm i energy even
at room tem peratures. F o r that reason the work function is pra ctica lly constant
over a w ide range o f temperatures.
250 Solids

E X A M P L E 6.3. Discussion of Pauli’s spin paramagnetism.

S o l u t i o n : The simple free-electron theory we have just discussed is enough to explain

many properties of metals, one of which is the small paramagnetism exhibited by most
metals. This paramagnetism was attributed by Pauli to a change in the states occupied
by the electrons with spin up and down when a magnetic field is applied, because the
magnetic field favors orientation of the electrons with their spins opposite to the field.

down

up

F ig. 6-23. Occupation of energy states

in the presence of an external magnetic
field.

We have seen (Section 3.6) that an electron carries a spin magnetic moment Pb and
that, in the presence of a magnetic field ® it acquires an energy ± p b ® , where the + ( —)
sign corresponds to spin up (down) or parallel (antiparallel) to the magnetic field. Given
that E is the total energy of the electron, the kinetic energy of the electron is E =F pb®,
depending on whether the spin is up or down. Therefore the occupation number of states
with spin up and down is

(S )1 - » + »»«■

where the factor £ enters because in each case we consider only electrons with the spin
in a given orientation. Figure 6-23 shows the graphs of (dn/dE) j and (dn/dE) [ (here
we assume that the temperature is close to absolute zero). W c see that the number of
electrons with spin down is greater than the number with spin up. N ote that we have
maintained the maximum energy equal to ( f . Even in the strongest magnetic fields used
in the laboratory (of the order of 0.1 T ), the energy p B® is about 6 X IO-6 eV, which is
very small compared with the Fermi energy, given in Table 6-1. Thus the two curves
are only slightly separated. Electrons with spin up contribute a magnetic moment —Pb
along the magnetic field, and those with spin down a magnetic moment + p b · Thus the
net magnetic moment per unit volume of the metal is

- Π - ® . --(a).] tF
dE

f
- £pb lg(E + mb®) — g (E — Mb®)] dE
Jo
re F

= P B ® [ -rL d E = p b ® ? (< f ).
Jo at
6.5) Electron motion in a periodic structure 251

In this calculation we have used the relation g (E ± μη®) = g (E ) ± μ „(B(dg/dE), de­

rived from Taylor’s expansion. RecallingEqs. (6.15) and (6.17), we have g(ey) = 3no/2cf,
and therefore the magnetization due to the spin reorientation is

9ΐΤ = ^ ® ,
zcf

which is in the same direction as ® and hence is a paramagnetic effect. The spin para­
magnetic susceptibility of a metal is thus

3ηομ£μο
Xm ~ 2eP '

Introducing numerical values with Cf ~ 2 eV , we get Xm ~ 5 X IO-6 . This value is in

agreement with the experimental result insofar as order of magnitude is concerned. A l­
though we made our calculation assuming a temperature close to absolute zero, the
result is valid for a fairly large range of temperatures.
Note from the above expressions that since in general no is larger and Cf is smaller for
d-electrons than for s- or p-electrons, the electron paramagnetism of atoms having in­
complete d-shells is larger.

fi.it E lo etron M o t io n in a E e rio d ie S truetu re

T o im p rove the free-electron m odel o f a solid, w e shall incorporate the effect o f the
periodic structure o f the lattice. L e t us start by first looking at the possible w ave
functions. I t is clear th at the effect o f the lattice isto change the free-particle w ave
function e 'k r so that, instead o f having a constant am plitude, this w a v e function
has a v a ry in g am plitude which changes w ith the period o f the lattice. T h erefo re
we w rite the w a ve function as

H r ) = eik'ru (r ), (6.18)

where u (r ) is a m odulating am plitude, repeating itself from one lattice cell to the
next. In the case o f a linear lattice o f spacing a, instead o f E q. (6.13) we must
w rite
H x ) = eikzu (x ), (6.19)

where u {x ) satisfies the condition

u (x + a) = u (x ). (6.20)

Expressions (6.19) and (6.20) taken togeth er constitute Bloch's theorem. (See
Exam ple 6.5 for a full p roof.)
W e m ay obtain a picture o f the w a v e functions (6.19) b y considering th at u (x )
resembles the w a ve function o f the isolated atom s and replacing e 'kx b y the w ave
functions o f a free p article in a poten tial box. Som e o f the w a ve functions for the
case of a lattice composed o f eight ions in a row are shown in Fig. 6-24. T h e band
252 Solids (.6.5

is composed o f eigh t levels, but on ly four w a v e functions are indicated. N o te

that, although the m om entum o f the electron described b y E q. (6.19) is n ot con­
stant, w e m ay still say th a t hk is a sort o f average m om entum o f th e electron
(see E xam ple 6.4). H ow ever, the w avelen gth associated w ith ψ (χ ) is still λ = 2 π /k,
and thus k is the w a v e number o f the electron.
T h e energy o f the electron is n ot entirely kinetic, as it is in the case o f the free
electron given b y E q. (6.11), because o f the poten tial energy due to the lattice ions.
T h e expression for the energy in term s o f k is com plicated and depends on the geom ­
e try o f the lattice. T h e im portant result is th a t the energy has a discontinuity or
gap a t certain values o f k which, for a linear lattice o f spacing a, are g iven b y

k — ηπ/α, n = ± 1 , ± 2 , .. . (6.21)

T h e graph o f E (k ) in this case is shown in F ig. 6-25. N o te from t h o graph th at for

values o f k n ot near those g iven b y Ecp (6.21), th e energy closely res'embles th at o f
a free particle (indicated b y the dashed line). T h erefo re the lattice affects the

JH
6.5) Electron motion in a periodic structure 253

E n ergy
bands
Jf -
I'irs t GriUouin zone

— Second B rillou in z o n e -

F ig. 6-25. BrilIouin zones in a linear lattice.

m otion o f an electron on ly when k is close to m r/a, and the effect is to produce

energy gaps. A t interm ediate values o f k, the electrons m ove freely through the
lattice. T h e allowed energy bands are those corresponding to the solid lines; these
energy bands are also shown at the right in the figure.
I t is not surprising th a t an electron can m ove freely through the lattice w ith ou t
encountering any resistance except when k is close to the values m r/a and the
perturbation o f the lattice is strong. T h e m otion o f the electrons in the lattice
can be considered as sim ilar to the propagation o f an electrom agnetic w a ve in a
crystal. T h e scattering o f the electrom agnetic w a ve b y the atoms in the lattice
gives rise to a reinforced scattered w a v e when B ra g g ’s condition is satisfied; th at is,

2a sin Θ = n\,

where a is the spacing between the planes and Θ is the angle th at the direction of
propagation makes w ith the lattice planes (F ig . 6-2 6). F o r norm al incidence

In cid en t S cattered
w a ves w a ves

F ig. 6-26. Bragg scattering.

254 Solids (6.5

(0 = τ / 2 ), B ra g g ’s condition becomes 2a = n\. T h is is the condition to be ap­

plied to a linear lattice for w a v e propagation along the lattice. F o r exam ple, if
w aves I and 2 (F ig . 6 -27) are reflected at successive ions A and A ', the reflected
rays I ' and 2' h ave a path difference 2a and a phase difference 27τ(2α)/λ. For
m axim um reinforcem ent o f I ' and 2', this phase difference must be equal to 2rnr,
resulting in 2α = πλ. S etting λ = 2 r/ k , w e obtain k = η ττ/a, in agreem ent w ith
Eq. (6.21). T h e refo re these values o f k are those a t which the linear lattice blocks
the m otion o f the electrons in a given direction b y forcing them to m o v e in the
opposite direction. T h e range o f A-values between — π/ a and - f x / a constitutes the
first B r illo u in zone. F o r k betw een — 2 ir/a and — π /a and between x / α and. 2π/α,
w e have the second B rillo u in zone, and so on.

Reflected ~ -a —
waves
2 ' ------------ --------
Incident ^ *■

A A'
F ig. 6-27. Bragg scattering in a linear lattice.

R eca llin g th a t the group v e lo c ity is defined by v„ = άω/dk (see A p p en d ix I I I )

and th at E = hu>, according to E q. (1.45), w e define the v e lo c ity o f the electron,
when it is represented by a w a v e packet centered about the energy E and w ave
number k as

_ I dE
( 6 .22 )
v ~ fi d k '

C om parin g this equation w ith the slope o f the curve in F ig. 6-25, we conclude th at
the v e lo c ity o f the electron varies w ith in the first B rillouin zone, as shown in
F ig. 6 -2 8 (a ), w ith sim ilar results for the other zones. T h e v e lo c ity is zero both
at the b o tto m and a t the top o f the band. A t in term ediate regions in the band, it
is v e r y close to the free-electron v e lo c ity , hk/m.

(b)
F ig. 6-28. Velocity and acceleration as a function of k in the first Brillouin zone of a
linear lattice.
 Electron motion in a periodic structure 255

G iven that F is the external force on the electron, the w ork done b y this force on
the electron during the tim e dt is Fv dt. T h is results in a change d E in the energy
o f the electron. Thus w e m ay w rite Fv dt = dE = (dE/dk) dk. Introdu cing the
expression for v given b y E q. (6.22), we obtain

F = h dk/dt. (6.23)

T h is can be taken as the equation o f m otion o f the electron in the lattice. C om par­
ing this equation w ith the classical equation o f m otion, F = dp/dt, w e conclude
th at hk plays the same role for electron m otion through a lattice under an external
force as the m om entum p plays for electron m otion in free space under the same
force. F o r th at reason hk is som etim es called t he lattice momentum o f the electron.
T o describe the m otion o f an electron (when it is represented by a w a v e packet)
as it m oves through the la ttice under an external force, w e m ust use both Eqs.
(6.22) and (6.23). E qu ation (6.23) gives the effect o f the external force on the
electron’s % a ve number k and Eq. (6.22) gives the v e lo c ity o f the electron result­
ing from that force plus the electron’s interaction w ith the lattice. L e t us first con­
sider an electron in the first B rillou in zone and suppose, for exam ple, th at the elec­
tron in itially has k = 0; th erefore its v e lo c ity is also zero. W hen the force F is
applied, k increases according to E q. (6.23), and from F ig. 6-28 w e see th at v also
increases; th at is, the electron accelerates. But when k reaches a certain valu e close
to Tc/a, the v e lo c ity begins to decrease (i.e., the electron decelerates even if the
force remains the sam e). T h is effect, o f course, is due to the interaction o f the elec­
tron w ith the lattice. W h en k = π/α, the v e lo c ity becomes zero but the w ave
packet representing the electron suffers a B ragg reflection in the lattice, k becomes
— Tc/a, and the propagation is in the opposite direction. O b viou sly the v elocity
now becomes negative. I f the applied force remains the same, Eq. (6.23) tells us
that k continues changing in the same direction, and therefore, since it is negative,
decreases in absolute value. F igu re 6 -2 8 (a ) indicates th at the v e lo c ity first in­
creases in a direction opposite to the external force, but v e ry soon its m agnitude
begins to decrease, since the force is opposed to the v e lo c ity ; i.e., the electron
decelerates, until even tu ally the v e lo c ity again becomes zero when k = 0. From
then on the cycle repeats itself. T h e acceleration o f the electron during the w hole
cycle is shown in Fig. 6 - 28 (b). Representing the state o f the electron by a d ot in
an E-versus-fc diagram (F ig . 6 -29), we can illustrate the process by m ovin g the
dot, as indicated b y the arrows in the figure. I f the electron starts at 0 , its repre­
sentative p oin t m oves from 0 to A , then jum ps to B and back to 0.
Let· us now consider an electron in the second B rillouin zone, which covers the
ranges — 2 π/α < k < — π/α and ir/α < k < 2ir/a. I f the electron initially has
a fc-value sligh tly above π/α, th e applied force increases the valu e o f k until
k = 2tr/α. A B ragg reflection suddenly reverses the m om entum and k jum ps to
the value — 2π/α. I f the force continues to act on the electron, k continues to
increase (actu a lly decreasing in absolute valu e) until it reaches the valu e — π/α,
when another B ragg reflection takes place and the m om entum is again reversed,
k changing to the valu e π/α. F rom then on the process continues in a cyclic
manner. H ence the electron describes the cycle C —* D —> E —> F —* C (F ig . 6-29).
256 Solids (6.5

F ig. 6-29. Electronic motion in first and second Brillouin zones in a linear lattice. Under
the action of an external force, the wave number and the energy of the electron vary within
a zone, as shown by the arrows.

F ig. 6-30. Velocity and acceleration as a function of k in the second Brillouin zone of a
linear lattice.
6.5) Electron motion in a periodic structure 257

T h e variation o f the v e lo c ity and the acceleration o f the electron in the second
Brillouin zone is shown in Fig. 6-30. Sim ilar logic applies to the other Brillouin
zones.
A n im portant conclusion to be derived from th e ab ove kinem atical description
is that an external force cannot rem ove an electron from a BrilIouin zone; there­
fore the electron remains in the same energy band unless enough energy is gained
in a single process (as b y absorbing a p hoton) to cross the energy gap and pass to
the next zone. (T h e re is, how ever, a certain p rob a b ility th at an electron under an
applied force w ill bridge the gap at k — ή ζη π / α ; this is called the Zener effect.
H ow ever, w e shall not discuss it here.)
I t has been found con ven ien t to define 5*
an effective mass m * of the electron accord­
ing to the relation m * = F /a. H e re F is
the external force applied to the electron
and o the actual acceleration due both to
F and to the lattice interaction. Thus we
cannot expect th at m * w ill be the same as
the electron mass TOc, nor should we ex- k
pect it to be a constant. C onsidering that

a = dv/dl = (dv/dk) dk/dt,

and using Eqs. (6.22) and (6.23), we have

Fig. 6-31. Effective mass as a func-

m (6.24)
d 2E / d k 2 tion of k.

N o te th at when the electron is free and its energy is given b y E q. (6.11), w e have
m * = TOe. O bviou sly to* is a function o f the param eters o f the lattice and o f the
electron’s lattice m om entum hk. F ro m the graphs o f /i-versus-k (F ig . 6-2 5), we
see that to* is p ositive at the b ottom o f an energy band and n egative at the top.
I t becomes v e ry large, actually infinite, at the inflection point o f the energy curve;
that is, at the m axim um o f v in Fig. 6-28. T h e variation o f to* w ith k in the first
Brillouin zone is shown schem atically in Fig. 6-31. T h e values o f in * a t the bottom
o f the energy band (a t k = 0) are given for certain m etals in T a b le 6-2.

T A B L E 6—2 Effective M ass

M ctal Li Na K Rb Cs

m*/me 1.40 0.98 0.94 0.87 0.83

W e shall com plete our description o f electronic m otion in a periodic lattice b y

considering the density o f states Q (E ) — dn/dE. W e have already discussed this
density for the free-electron m odel [E q. (6.15) and Fig. 6-20]. A t the bottom of
258 Solids (6.5

the band th e d ensity o f states closely resembles the parabolic curve o f the free-
electron m odel, but instead o f increasing steadily, the curve decreases alm ost
p arabolically at the top o f the band. T h is is shown in F ig. 6-32, w hich m ust be
considered as on ly qu a litative. T h e actual shape o f dn/dE depends on the struc­
ture o f the lattice and the position o f the band. T h is m ore or less sym m etric shape
o f dn/dE can be easily understood. Suppose th at a band is com pletely filled. If
one electron is rem oved (perhaps to the conduction band), it is possible to say
th at a hole has been created, since there is now a vacan t s tale in the band. W h en
an external force (such as an electric field) is applied, some electron m ay be m oved
into the vacan t state, th ereby filling the hole. B u t in so doing, this electron leaves
a new hole in the band corresponding to the state it previou sly occupied. W e can
say th a t the hole m oves in a m anner exa ctly opposite to th at o f the electrons
under the applied force, and thus acts as a p ositively charged particle. T h e zero
o f energy for the holes is at the top o f th e band and th eir energy is measured d ow n­
w ard ; th a t is, Fmax — E . T h erefo re d n/dE a t the to p o f the band is v e ry sim ilar
to E q. (6.15), but w ith E replaced by Fmax F.

dn
dE

F ig. 6-32. Density of energy states

in a band.

0 «K
P
T h e student m a y realize th at in our d escriptive analysis o f electron m otion in
a periodic lattice, w e have blended the quantum and classical pictures o f the elec­
tron. W e h ave done this in order to obtain the basic results desired w ith ou t be­
com ing in vo lved in com plex quantum -m echanical calculations which are beyond
the scope o f this book.

E X A M P L E 6.4. Calculation of the average value of the momentum of an electron

described by the wave function φ = e'klu (x ).

S o lu tio n : Assuming that the wave function φ (χ ) is normalized to unity, we have

j φ*φ dx - J u * u dx = I.

Applying Eq. (2.50), we may write the average momentum of the electron as
6 .5 ) Kledrori mol ion in a periodic structure 259

But

and, since Φ* = ce ikxu

,kxu *(x
* (x),), we obtain

Because the normalization condition makes the first integral on the right equal to I, we
may write

where p„,aVe corresponds to the second term, and may be considered as the average
momentum of the electron as a result of its interaction with the ions forming the lat­
tice, since this is the physical meaning we have attributed to « ( z ) . In this way we con­
clude that the average momentum of the electrons is composed of tw’o parts: the lattice,
or quasi-free, particle momentum hk and the momentum due to the interaction with the
lattice.

E X A M P L E 6.5. Proof of Bloch's theorem, which states that u (x ) in Eq. (6.19) is a peri­
odic function with the same period as the lattice spacing.

S o lu tio n : Let us consider a linear lattice of spacing a, such that E p(X) = E p(x + a).
Then, since the probability distribution of the electrons must show the same periodicity
as the potential energy, we may write

\i(x)\2 = \ψ(χ + <i)|2. (6.25)

Equation (6.25) implies that φ (χ + a) = Οψ(χ), where C is a quantity satisfying the

condition |C|2 = I. Thus we may write C = eika, where k is an arbitrary parameter.
Then we have the following:

Multiplying both sides of the equation by e ,kx, we obtain

e ~ ikxifi(x) = e ~ 'kt-x +<"4r(x + a).

This shows that u (x ) — e~ iir^/{x) is a periodic function of x, with period a. By writing

ψ{χ) = eikxu (x ), we then have Bloch’s theorem.

E X A M P L E 6.6. Calculation of the width of an energy band using the so-called light-
binding approximation.

S o lu tio n : A convenient approximate wave function— called the tight-binding approxi­

mation— for an electron moving in a linear lattice of spacing a is

(6.26)
260 Solids C6.5

where φ is the atomic wave function of an electron in a stationary state of an isolated

atom and n — 1 ,2 N identifies each of the atoms in the lattice. Thus φ (χ — na)
is the wave function corresponding to the nth atom and φ is a linear combination of
atomic wave functions with convenient phase factors. This wave function corresponds
to the description given in Fig. 6-24. Before proceeding to calculate the band width, we
must verify that Eq. (6.26) satisfies Bloch’s theorem. The wave function φ may be
written in the form

φ = eikt Y j e- ,t<1—"0V ix - na)

n

which, by comparison with Eq. (6.9), gives

u (x ) — Y 1 β~'Η*~ ηα)φ(χ — na).

n

Then
u{x-\- a) = Y j β,*Ιι~ ί’ι~ 1>α1φ[χ — (η — l)e ],
n

I f the number N of atoms which constitute thelattice isvery large sothat we may dis­
regard theend effects, the summations appearing inbothexpressions of u are identical
and u (x ) = u (x + a), as required by Bloch’s theorem.
T o find the average energy of an electron described by the wave function (6.26), we
apply Eq. (2.51); that is,

£‘ n = % 4 d x ’ (6 27)

where H is the hamiltonian operator of the electron, given by

and E p(x ) is the periodic potential energy of the electron in the lattice. A straightforward
calculation, which we omit, gives

E ave = Eat — ot — 2/3 cos ka (6.28)

where Ent is essentially the energy of the atomic state associated with wave functions
φ(χ — na) and a and /3 are appropriate constants. Equation (6.28) shows that the values
of Eavc are between E l l — a — 2/3 and E„t — a + 2/3, depending on the value of k. In
other words, the width of the band is 4/3. The values of E, a, and β depend on the atomic
state through the wave functions φ; therefore there are a series of energy bands, each
correlated with an atomic state. Figure 6-33 shows the expression (6.28) plotted for
several bands. The portions corresponding to each of the Brillouin zones are indicated
by heavier lines. The frce-particle energy is also shown by the dashed parabola. Note
the similarity to Fig. 6-25. Instead of choosing several ranges of k to express the Bril-
louin zones, we could have limited k to the range —π/β < k < ττ/α for all bands and
used only the central portions of the curves for the different zones.
6.6) Conductors, insulators, and semiconductors 261

F ig . 6-33. Allowed energies in the tight-binding approximation.

li.ti t'om iuctorH, I nsnlalors. anti Svm U'onduetorH

An interesting property o f solids is their electrical conductivity. Som e materials,
traditionally called insulators, are extremely poor conductors o f electricity
(examples are diamond and quartz and, in general, m ost covalent and ionic solids).
Other solids are exceedingly good conductors o f electricity; in this group fall the
metals, such as copper and silver. (T o get a quantitative idea, consider copper,
whose electrical conductivity at room temperature is IO20 times greater than that
of quartz.) Intermediate between these tw o extreme groups is a third class of
solids, called semiconductors. Although sem iconductors arc much poorer electrical
conductors than the metals, their condu ctivity increases w ith the temperature,
while that o f metals decreases w ith the temperature. T ypical sem iconductors
are germanium and silicon.
One of the most im portant reasons for the initial success o f the band theory of
solids was that it offered a simple explanation of this markedly different electrical
behavior o f solids. W e shall make our first analysis by means o f the frec-clectron
model, which we shall later refine by taking into account the periodic structure of
the lattice.
262 Solids (6.6

L e t us consider a m etal havin g the band structure shown in Fig. 6-34, which
m igh t correspond, for exam ple, to the energy levels o f sodium (Z = 11). Bands
corresponding to the Is, 2s, and 2p atom ic levels are com pletely filled because the
respective atom ic shells are also com plete. B u t the 3s band, which can accom ­
m odate up to tw o electrons per atom , is on ly half filled, since the 3s level in each
sodium atom has on ly one electron. D u e to therm al excitation, some electrons
in the 3s band, which have an energy o f the order o f the F erm i energy for this
band, pick up energies of the order o f k T (abou t 0.025 e V at room tem perature)
and their distribution am ong th e energy states o f the band resembles th at o f
F ig. 6-22. U n der the action o f an external electric field, these electrons m ay,
w ith ou t vio la tin g the exclusion principle, pick up additional small amounts o f
energy and pass to any o f the m any nearby e m p ty states within the band. In
sharp distinction to disordered therm al excitation, the electrons excited b y the
electric field gain m om entum in the direction opposite to the field; this results in
a collective m otion through the crystal, which constitutes an electric current.
T h erefo re w e conclude that a substance having a band structure such as th at o f
F ig. 6-34 should be a good conductor o f electricity, and for the same reason it
should be a good therm al conductor, w ith the electrons in the upperm ost par­
tia lly occupied band being responsible for both processes. In other words, the good
conductors o f electricity (also called metals) are those solids in which the upper­
m ost occupied band is n ot com pletely filled.

Empty
" band

I H a lf-
F ig. 6-34. Energy bands in a con­
ductor.

In n er
filled
2s: bands
Is -

A c tu a lly the situation is sligh tly m ore com plex because o f the possible super­
position o f the upperm ost bands. F igu re 6-35 shows the actual band structure of
sodium. A t the equilibrium distance r 0 in the m etal, about 3.67 X IO-1 0 m, the
2p level remains p ractically undisturbed, but the bands corresponding to the 3s
and 3p atom ic levels overlap. T h erefo re the conduction electrons have m any
m ore states availab le than those corresponding to the 3s band alone. In fact, this
overlap pin g o f the outerm ost bands is the com mon situation for m ost m etals or
conductors. F o r exam ple, consider the case o f magnesium ( Z = 12). T h e m ag­
nesium atom has the configuration I s 2 2s2 2 p e 3s2, and therefore all the atom ic
shells are filled. H ow ever, the first excited level, 3p, is rather close to 3s. In the
6.6) Conductors, insulators, and semiconductors 263

D -3d

-10

s -2 0 -

0 3.67 5 10
In tern u clea r distance, IO-10 I

F ig. 6-35. Energy bands of sodium.

solid state the band structure is similar to th at o f F ig. 6-35 for sodium. T h e 3s
and 3p bands are indicated schem atically in Fig. 6-36. N o rm a lly , w ith no over­
lapping, the 3s band should be filled and the 3p band em pty, and magnesium should
be an insulator, as explained below. B u t because o f the overlappin g, the upper­
m ost electrons o f the 3s band have the low est energy states o f the 3p band a v a il­
able. Thus some 3s electrons m ove to occupy som e low 3p-levels until an equilib­
rium energy level for both bands is established. Since the total number o f energy
levels availab le from the 3s and 3p bands is 2.V -)- 6iV = 8.V and w e h ave on ly
2N electrons, there are 6N accessible em p ty states. T h erefo re m agnesium should
be a good conductor; this is in agreem ent w ith the experim ental facts. T h ose sub­
stances whose atom s have com plete shells but which, in the solid state, are con­
ductors because o f the overlap pin g o f a filled band and an e m p ty band are often
called semimetals.

■3p

3s
F ig. 6-36. Overlapping of energy
bands in a conductor.

"2 p
 264 Solids (.6.6

Con du ction
M m nd
J (em pty)
_ Im rge
en erg y gap

Ω
dn
dE
V alen ce
M m nd
J (fille d )

F ig. 6-37. Energy bands of an insulator. F ig. 6-38. Energy band structure for
diamond (C ) 1 silicon (Si), and germanium
(G e).

I n the transition m etals group, such as iron, the overlap pin g bands are 3d, 4s,
and 4p, and the number o f electrons is insufficient to fill these bands. Sim ilarly,
in the rare-earth group, the overlap pin g bands in vo lved are 4f, 5d, 6s, and 6p.
H ence these elements, when in the solid state, are conductors.
L e t us now consider the case o f a substance in w h ich the uppermost or valence
band is com p letely filled and does not overlap the next band, which is to ta lly
e m p ty (F ig . 6 -3 7 ). Since all states o f the valence b a w f are occupied, the electron
energy is “ fro zen ,” th at is, the electrons cannot change their state w ith in the band
w ith ou t vio la tin g the exclusion principle. T h e on ly possibility for exciting an elec­
tron is to transfer it to the e m p ty conduction band; but this m a y require an energy
o f a few electron volts. H ence an applied electric field cannot accelerate th e elec­
trons in the valence band, and thus cannot produce a net electric current. T h is
substance is therefore an insulator. (O f course, at a su fficiently high tem perature
or under v e r y strong electric fields, some electrons m ay be excited to the conduc­
tion band, and then an electric current is possible.) M o s t covalen t solids, w hich
are composed o f atom s h avin g an even number o f valence electrons, are insulators.
Figure 6-38 shows a sim plified band scheme of diam ond ( C ) . T h e bands correspond
to the atom ic 2s and 2p levels in diam ond, which can accom m odate up to 8 elec­
trons. H o w ever, the carbon atom has on ly 4 electrons available for these levels
(rem em ber Figs. 4-7 and 4 -1 0 ). A s the atom s g e t closer, the 2s and 2p bands
begin to overlap. A t smaller inter-atom ic distances, th ey sp lit again into tw o bands,
each accom m odating up to 4 electrons per atom. (T h is conclusion is arrived at
by a detailed calculation.) H ence the 4 electrons from each atom are norm ally in
the low er or valen ce band, w h ile th e upper band is em pty. A t the equilibrium
distance in diam ond, about 1.5 X IO-10 m (ind icated by C in Fig. 6 -3 8 ), the gap
separating the low est or valence band from the upper e m p ty band is about 5 eV.
T h is m ay be considered as a r e la tiv e ly large energy gap ; it explains w h y diam ond
is such a good insulator.

I, j
6.6) Conductors, insulators, and semiconductors 265

Con du ction
band

Sm all
Fig. 6-39. Energy bands and en ergy gap
electron distribution in a semi­
V alen ce
conductor. band

T h e sameafaand scheme also applies to silicon and germ anium (excep t th a t the
bands correspond to differen t atom ic energy levels and en ergies); the equilibrium
separation o f the atom s in their solid states is also shown in F ig. 6-38. N o w , how­
ever, the gap between the valence and conduction bands a t the equilibrium separa­
tion o f the atom s is much sm aller (1.1 e V in silicon and 0.7 e V in germ anium ), and
this makes it much easier to excite the upperm ost electrons in the valence band into
the conduction band. T h e situation is illustrated in F ig. 6-39. A s the tem pera­
ture increases, m ore electrons are able to ju m p into the next band. T h is has tw o
results: T h e few electrons in the upper or conduction band act as th ey would in a
m etal, and the em p ty states, or holes, left in the low er or valence band act in a
similar w ay, but as if th ey w ere p ositive electrons (also, their effective mass m ay
be d ifferent because th ey are in a differen t energy band). Thus w e h ave electric
conduction from the excited electrons in the conduction band and from the holes
in the valence band; the con d u ctivity increases rap id ly w ith the tem perature b f
cause m ore electrons are excited to the conduction band. F o r exam ple, in silicon,
the number o f excited electrons is increased b y a factor o f IO6 when the tem pera­
ture is raised from 250 0K to 450 °K . H ence semiconductors are insulators in
which the energy gap betw een the valence band and the conduction band is about
one e V or less, so th a t it is re la tiv ely easy to th erm ally excite electrons from the
valence to the conduction band. T h e energy gaps o f som e insulators and semi­
conductors are g iven in T a b le 6-3.

T A B L E 6-3 E n ergy G a p s (e V )

Insulators eV Semiconductors eV

Diamond 5.33 Silicon 1.14

Zinc oxide 3.2 Germanium 0.67
Silver chloride 3.2 Tellurium 0.33
Cadmium sulfide 2.42 Indium antimonide 0.23

T h e electrical conduction in sem iconductors w hich w e have described is called

in trin sic conductivity. T h e con d u ctivity o f a sem iconductor can also be enhanced
b y the ad dition o f certain im purities. Suppose th at w e replace som e o f the atom s
o f the sem iconductor b y atom s o f a different substance (these atom s then constitute
266 Solids (.6.6

LConduction Conduction
t I J
T___
I band
} band
•w

111
III
I I
III

II

I I
III
II
■*— Impurity levels
II

— — — f——— ——f— —
L Valence ί 4 I L Valence
J band J band

(a) (b)

F ig . 6—tO. Impurities in a semiconductor: (a) donors, or n-type, (b) acceptors, or p-type.

the im p u rity ), and suppose th at these im pu rity atom s have more electrons than
those o f the semiconductor. F o r example, if to silicon or germ anium , w hich con­
trib u te four electrons per atom to the valence band, vve add a few atom s o f phos­
phorus or arsenic, each o f w hich contributes five electrons per atom to the valence
band, w e have an extra electron per im pu rity atom. These additional electrons
(w hich cannot be accom m odated in the valence band o f the original lattice) occupy
some discrete energy levels just below the conduction band; the separation m ay be
a few tenths o f an eV (F ig. 6 -4 0 (a )l· These excess electrons are easily released by
the im pu rity atom s and excited into the conduction band. T h e excited electrons
then contribute to the electrical con d u ctivity of the semiconductor. Such im pu rity
atoms are called donors; the semiconductor is called an n -type (o r n egative)
semiconductor.
C onversely, the im pu rity m ay consist o f atoms havin g fewer electrons than those
o f the semiconductor. F o r the cases in which silicon and germ anium are the host
substances, the im pu rity atoms could be boron or aluminum, each o f w hich con­
tributes on ly three electrons. In this situation the im pu rity introduces vacant
discrete energy levels, v e ry close to th e top o f the valence band (F ig . 6 - 4 0 (b )).
T h e refo re it is easy to excite some o f the more energetic electrons in the valence
band into the im pu rity levels. T h is process produces v acan t states, or holes, in
the valence band. A s explained previou sly, these holes then act as p ositive elec­
trons. Such im pu rity atom s are called acceptors; the sem iconductor is called a
p -typ e (o r p ositive) semiconductor.
T o produce significant changes in the con d u ctivity o f a semiconductor, it is
sufficient to have about one im pu rity atom per m illion sem iconductor atoms.
Sem iconductors have a w ide industrial application as rectifiers, m odulators, detec­
tors, photocells, transistors, etc.

E X A M P L E 6.7. Discussion of the p-n junction.

S o lu tio n : One important application of semiconductors to modern electric circuitry is

the p-n junction. Suppose that we have two samples of the same semiconductor— say
germanium— one of p-type and the other of n-type (F ig. 6—41 fa )) . I f the two samples
are placed in contact (F ig. 6 -4 1(b )), there is a diffusion or flow of holes from the left to
the right and of electrons from the right to the left. This double flow produces a double
layer of positive and negative charges on both sides of the junction, setting up a potential
6.6) Conductors, insulators, and semiconductors 267

o : holes (positive)
(a) • : electrons (negative)

O · 0 ·
Oo 0 ·
0

• 0
0
•

0 0 · ° · ·
(b)

0 ·ο ° 0· · —
«O* In
o ° .s
O o · L · 0 · ··
eο (c)

(d)

F ig. 6-41. The p-n junction.

difference across the junction [as shown on the right in part (b )] which, when equilibrium
is reached, opposes the further flow of holes and electrons across the junction. In the
succeeding discussion we shall concentrate on the holes; the situation for the electrons
is equal and opposite.
Due to the recombination of holes and electrons, the number of holes in the n-type
semiconductor tends to decrease, which allows a small hole current l\ to flow contin­
uously from the p-side to the n-side. A t the same time, due to thermal excitation, hole-
electron pairs are produced in the n-type semiconductor, and these excess holes can flow
very readily across the junction into the p-side with a current 12 · A t equilibrium both
hole currents are identical; that is, /1 = 12 (similar logic can be applied to the electrons).
268 Solids {6.7

I f a potential difference V is applied, as in Fig. 6—41(c ), with the p-side joined to the
positive terminal and the n-sidc to the negative terminal of the source of V, the height of
the potential difference across the junction decreases. This allows a larger current I i to
the right, without actually changing the thermally generated current /2 to the left. Thus
a net hole current I i — /2 results across the junction to the right, and this current in­
creases very rapidly with V, due to the large supply of holes from the p-side. On the
other hand, if the potential difference V is reversed, as in Fig. 6-41 (d), the potential dif­
ference across the junction increases. This reduces the value of 11, again without sub­
stantially affecting 12 , since the supply of holes from the n-side is temperature limited.
Thus a net current to the left will exist across the junction which will approach the
constant value 12 with increasing V .

I = I i- I 2

F ig. 6-42. Current as a function of voltage across

a p-n junction. The voltage V is considered positive
when applied in the direction p —> n and negative
when applied in the opposite direction.

Figure 6-42 shows the graph of the net current across the junction as a function of V,
with V considered positive when applied as in Fig. 6-41 (c) and negative otherwise. The
net current is expressed fairly accurately by the expression

I = /1 - /2 = I 2(eVlkT - I).

W e conclude that a p-n junction acts as a rectifier or a detector device favoring the
passage of a current in the direction p —» n. This is the same function performed by
diode and triode electron tubes, but the p-n junction may perform it with an expenditure
of considerably less energy.

6 .7 H u a n tu m Thpwry o f E le e trira l C o n d u etirity

In the preceding section we have discussed electrical conduction in solids from the
p oin t o f v ie w o f the free-electron model. T h e periodic structure o f the solid must
be taken into account, how ever, and the results o f Section C.5 must be used in
order to obtain qu a n tita tive results. F or sim plicity, w e shall base our discussion
on a one-dim ensional model. L e t us consider the solid to be in its ground state,
6.7) Quantum theory of electrical conductivity 269

E E

k
O O
a a a
o tio n to le ft M o tio n to right M o tio n to le ft M o tio n to righ t

(a) (b )

F ig. 6-43. Occupation of energy levels in the first Brillouin zone: (a) no electric field
applied, (b) external electric field applied from right to left.

w ith no electric field applied, and assume th at the electrons are in the first Brillouin
zone (th e same logic, how ever, applies to any other zone). T h e electrons are occupy­
ing the low est states w ith in the band, in a sym m etric form , so th at no net current
exists (F ig . 6 - 4 3 (a )). I f an electric field is applied, all electrons experience a force
in a direction opposite to th e field and, according to E q. (6.23), th eir fc-values in­
crease in the direction o f the force. T h e result is an asym m etric distribution o f the
electrons w ith in the m etal, as shown in F ig. 6 -4 3 (b ). T h is g ives rise to a net
electric current in the m etal, since m ore electrons m ov e in one direction than in
the opposite direction.
A s long as the electric field is applied, the occupation o f states w ith k parallel
to the force increases w ith tim e and the occupation o f those states w ith k opposite
decreases w ith tim e. In other words, the current increases continuously w ith
time, even if the electric field is constant, due to the continuous acceleration o f the
electrons. (W e shall ignore th e com plex effects th at m ay result when som e elec­
trons even tu ally reach the boundary o f the B rillouin zone a t fc = ττ/α; this problem
has previou sly been discussed in Section 6.5.) T h e ab ove result contradicts experi­
ence. M o s t conductors ob ey O hm ’s law, w hich m ay be w ritten either in the
fam iliar form V = R l or in the m ore convenient form

j = σ δ, (6.29)

where j is the current density, expressed in A m - 2 , 6 is the applied electric field,

expressed in N C - 1 , and σ is the conductivity o f the substance, expressed in Ω-1 m —'.
T h e reciprocal o f the con du ctivity,

P = Ι/σ', (6.30)

is called the resistivity, and is expressed in Ω m.

In either of the tw o forms, O hm ’s law states th at a constant electric field produces
a constant electric current; th at is, when an electric field is applied, the conduction
270 Solids (6.7

electrons in a m etal acquire an average and constant d rift velocity. T h erefo re we

conclude th at there must be some mechanism which prevents the electrons under
the applied electric field from acceleratin g indefinitely up to the top o f the con­
duction band.
In the classical theory, form ulated by D rude and L oren tz before the advent o f
quantum theory, this constant average v e lo c ity o f the electron resulted from the
frequ en t collisions o f the electrons w ith the p ositive ions which constitute the
m etal lattice. In such collisions, an electron was supposed to transfer the m om en­
tum it had gained from the electric field since the previous collision to the ion, and
this prevented the electron from being accelerated continuously as it drifted in
the direction opposite to the applied electric field. T h is mechanism also explained
the Joule effect as being due to the energy gained b y the ions from the electronic
collisions. In the D ru d e-Loren tz theory, the con d u ctivity is given by

σ = ne2T/mc, (6.31)

w here n is the number o f electrons per unit volu m e and r is a param eter called the
relaxation time. T h is expression can be derived as follows. T h e acceleration o f an
electron due to the applied electric field is a = — eS/?nc. I f I is the tim e between
tw o successive collisions o f the electron w ith the lattice ions, the average d rift
v e lo c ity o f the electron is Vt v e = ja l = — e(6)t/2m,.. T h e current density is then
j = -C T ivtve = (n e 2l/2me)S , which yield s σ = ne2t/2m0. Com parison w ith
E q . (6.31) shows that r = %t. H ence in the D ru d e-Loren tz th eory the relaxation
tim e r is assumed to be o f the same order o f m agnitude as the tim e between tw o
successive collisions o f the electron w ith the ions o f the lattice. F o r most m etals
at room tem perature, the valu e o f r, com puted from the measured valu e o f σ, is
o f the order o f IO-14 s. G iven th at I is the avera ge separation o f the ions and v,
is th e average therm al v e lo c ity o f the electrons in the absence o f the electric field,
w e can assume that the relaxation tim e is o f the order o f m agnitude o f l/vt. F o r
most solids I is o f the order o f IO- 9 m. Using for th e electrons the same relation
d erived for gas molecules, vt = \/3kT/m e (see Section 10.6), w e find th a t at room
tem perature v, is o f the order o f IO5 m s - 1 . T h en I fv l ~ IO-14 s, in agreem ent
w ith the experim ental valu e o f r. H o w ever, at tem peratures th at are low (but
n ot too close to absolute zero), the con du ctivity o f m etals varies approxim ately
as the reciprocal o f the absolute tem perature (th a t is, σ ~ l / T or p ~ T ) , as
shown in F ig. 6—14 for sodium. T h is means th at the relaxation tim e also varies
reciprocally w ith th e tem perature.
W hen w e com pare the experim ental valu e o f r at low tem peratures w ith th at of
l/vi, in order to obtain a qu a n tita tive agreem ent w e would have to assume values
fo r I m any times larger than the interionic separation. T h is w as one o f the first
clues th at the D ru d e-Loren tz theory was not correct.
H en ce w e shall first try, using the quantum theory, to explain w h y the elec­
trons m aintain a constant average v elocity , and next obtain a qu a n tita tive expres­
sion for the con du ctivity, sim ilar to E q. (6.31).
In the quantum theory, an electron is represented by a w a ve packet. T h e re is
an en ergy spread centered about the energy E and an associated wave-num ber
6.7) Quantum theory of electrical conductivity 271

spread centered about the w a v e number A-. T h e m otion o f a w a ve packet m ay be

hindered by scattering. In itia lly the w a ve packet is m ovin g in a particular direc­
tion w ith the w a ve number A ; a fter the scattering it is m ovin g w ith a different
w ave number, say A·', in a different direction. In other words, scattering produces
a transition A· —> A'. In the transition, some m om entum and energy are transferred
to the scatterer. Th&^effect o f the applied electric field is to accelerate the electrons
in a certain direction; the effect o f the scattering is to disarray the electron m otion,
hindering the accelerating effect of the electric field.

S cattering
in to e m p ty states

Fig. 6—14. Variation of resistivity with F ig. 6-45. Scattering of electrons in first
temperature. Brilloiiin zone by impurities.

A steady state is produced when these tw o effects balance each other, in a sta­
tistical sense, resulting in a constant average v e lo c ity o f the conduction electrons.
F or this situation to exist, the scattering m ust occur at any A-value within the
conduction band. Consider, for example, the one-dimensional case shown in
Fig. 6-45, which is sim ilar to F ig. G -43(b). Since scattering cannot v io la te the
exclusion principle, the electrons must be scattered into va c a n t states. Thus the
elect rons that are ,scattered are t he most energetic ones. These elect rons are
scattered into va c a n t states which, in a linear lattice, have opposite m om entum
and (in gen eral) low er en ergy; the figure indicates this schem atically. T h e energy
lost by the electron is absorbed by the scatterer. T h e result is that the most ener­
getic electrons frequ en tly reverse their m otion, thereby checking the accelerating
effect o f the electric field. T h e number o f electrons m ovin g to the right and to the
le ft is m aintained at a statistically constant difference, g ivin g rise to a steady cur­
rent. A lth ou gh w e h a ve used a one-dim ensional m odel, a sim ilar situation exists
for the three-dim ensional case. W e t hen see that the idea o f scattering o f the elec­
tron w a v e packet accounts for both Ohm ’s law and the Joule effect. T h e latter
results since energy and m om entum are transferred to the scatterers.
272 Solids (6.7

Since w e h ave previou sly seen (Section 6.5) th a t an electron can m ove freely
through a crystal lattice (excep t when k = ± 7 r / a ), our next task is to id en tify
the sources o f the assumed scattering. T h e general answer is the follo w in g: any
irregu larity in the p eriodicity o f a lattice disturbs the otherw ise free m otion o f
the electron, and the disturbance can be considered as a scattering. These lattice
irregularities are due to tw o factors: ( I ) I mperfections in the solid, such as vacant
spaces, interstitial and displaced atoms, dislocations, and im purities; for exam ple,
if small amounts o f im pu rity atom s are added, and these are un iform ly distributed
throughout the solid, the con du ctivity is m odified. T h e contribution to the con­
d u c tiv ity due to scattering by im perfections in the lattice is essentially independent
o f tem perature. (2 ) Therm al oscillatory m otion o f the ions w hich constitute the
lattice. Since the ions do not all oscillate in phase, their vibrations g iv e rise to small
fluctuations in the lattice spacing; although these fluctuations are small, th ey are
spread over all the lattice. In addition, because the oscillations increase the effec­
tiv e cross section which the ions present to the m otion o f the electrons, the prob­
ab ility o f scattering is prop ortion ately larger. C lea rly the lattice-vib ration effect
is tem perature-dependent, since the am plitude o f the vibrations depends on the
vibration al energy and this in turn depends on the tem perature.
T o be m ore qu a n tita tive, w e m ay still use E q. (6.31) to express the conduc­
tiv ity , replacing the electron mass mc by its effective mass m * ; th at is,

σ = ne2T/m*. (6.32)

In general w e can calculate m * at the F erm i en ergy «κ, since the energy o f the
conduction electrons is not v e ry differen t from e F. A lso n is not the to ta l number
o f electrons per unit volu m e in the conduction band; rather it is the effective
number o f electrons which p articipate in the conduction. T h is number is smaller
than the total number of electrons in the conduction band, due to the restrictions
imposed by the exclusion principle.
G iv e n th at P , is the prob ab ility o f scattering o f the electrons per unit tim e (thus
it is expressed in s- 1 ), the relaxation tim e is given by

r = I / P .. (6.33)

In other words, the larger the scattering p rob ab ility, the sm aller the relaxation
tim e and the sm aller the con du ctivity, as our physical m odel requires. L e t us
designate the scattering p ro b ab ility per unit length b y Σ , (thus it is expressed in
m ~ ‘ ). T h is q u a n tity is also called the macroscopic scattering cross section. The
conduction electrons m ove w ith a v e lo c ity v e ry close to th at corresponding to the
F erm i energy eF. D esignating this v e lo c ity b y e F, w e have that P , = t’F2 s, and
E q . (6.33) becomes

T = l/ c F2,. (6.34)

T h e problem has thus becom e one o f calculating 2,. T h is is a difficult problem

w h ich is beyond the scope o f this text. H ow ever, we can m ake certain estimates.
6.7) Quantum theory of electrical conductivity 273

I t is natural to assume th at Σ , is proportional to the number o f scattering centers

per unit volum e, designated b y n , (expressed in m ~ 3), and so w e m ay w rite
2, = η ,σ ,, where σ , (n o t to be confused w ith t he con d u ctivity) is called the scat­
tering cross section per center (it is expressed in m 2).
W e can calculate σ„ b y using the techniques o f quantum mechanics if w e know
the interaction between the electron and the scatterer. T h e F erm i v e lo c ity Vp is,
by definition, tem perature independent. Also, in the case o f lattice im perfections,
the term s appearing in 2 , are basically tem perature independent. Thus we v e rify
that the con du ctivity due to lattice im perfections is independent o f the tem pera­
ture. On the other hand, it is reasonable to assume (and it can be shown theo­
retica lly) that for lattice v ib ra t ions σ » is proportional to the square o f the am plitude
o f the ion oscillations; th at is, a s ~ A 2. B ut the energy o f an oscillator is propor­
tional to the square o f the am plitude, and we m ay w rite

a s ~ vib ration a l energy.

A t tem peratures not too close to absolute zero, the average vib ration al energy of
a solid is proportional to the absolute tem perature T . T h erefo re w e conclude th at
σ , ~ T , which, according to E q. (6.25), means th at τ ~ I / T . T herefore, in v ie w
o f E q. (6.23), w e have that σ ~ I / T . W e thus v e r ify th at the con d u ctivity due to
lattice vib ra t ion has the proper tem perature dependence.
I f 2,.,· is the m acroscopic cross section due to the im purities and 2 , i( is th at
due to the th erm al vib ration s o f the lattice, w e have 2 , = 2,.,· + 2 ,,t) so long as
we m ay assume th at the tw o scattering probabilities are ad ditive. T h erefore
I/ r = νρΣ, = AfQSj,i + £,.<), and w e m ay w rite the resistivity o f the m etal as

I m *v F , .
P — σ
~ — -■n £e
o ." (2 J.*' + 2 ».i) = Pi + Po (6.35)

where p, is the resistivity o f the m etal due to the im purities and therefore is essen­
tia lly tem perature independent (b u t varies from one specimen to another), and
Pt is the resistivity due to therm al vib ration s; p, increases w ith the tem perature
and is the same for all specimens of the
same m etal. E qu ation (6.35) expresses a
well-known experim ental result, known
as Mathiessen’s rule. T h e qu an tity p,- is
called the residual resistivity. Figure 6-46
shows the resistivity o f three specimens of
sodium w ith different im purities in a
tem perature range below 20 °K . The
curves show the v a lid ity o f E q. (6.35).

Fig. 6-46. Resistivity of three different

samples of sodium. [Adapted from D. Mac­
Donald and K. Mendelssohn, Proc. Roy. Soc.
(London) A202, 103 (1950)] T em p eratu re, 0K
274 Solids (6.8

G.tt K a d i a t i v e TranH itionM in Solitls

So far w e have developed a m odel o f solids, the band theory, which accounts for
m ost properties o f solids in a consistent fashion; this, o f course, is the m ost a
physicist m ay expect from a model. B ut is there an y direct evidence o f the exist­
ence o f energy bands and energy gaps? Is it possible to measure the F erm i energy?
T h e answer to these questions is yes. Perhaps the m ost direct evidence comes from
rad iative transitions in solids. W e shall first discuss x-ray emission and then some
absorption processes.

~ * r a s i
F ig. 6-47. X -ray electronic transition
from the uppermost band into a vacant
inner atomic state; (a) conductor, (b) in-
s u la t o r · In n er
atom ic <-
level
(a)

X -ra y emission in atom s results when an electron occupying one o f the outer
shells falls into a v acan t state le ft in one o f the inner or low -lyin g inner shells
(Section 4.7). A ccord in g to the band th eory, we m ay say that x-ray emission in
solids takes place when, for example, an electron in the upperm ost band undergoes
a transition into a low er-level band where a va c a n t state exists, as indicated in
F ig. 6-47. These vacan t states are produced by electron bom bardm ent or by ab­
sorption o f radiation. T h e low est or final energy le v el in the transition is prac­
tic a lly identical w ith the atom ic energy levels since, as explained before, such
levels are not affected when the solid is formed.
In the atom ic case, a given transition corresponds to initial and final energy
levels o f well-defined energy, resulting in a photon o f a certain energy or a sharp
line o f a given w avelength. B ut the band th eory suggests a d ifferent situation in
the case o f solids. T h e electron m aking the transition can start from any o f the
possible energy levels in the upperm ost band, and therefore the energy o f the
em itted photons has a spread o f the order o f « f (th a t is, the photons have energies
between E 0 and about E 0 4- €p). In the case o f an insulator, the energy spread
is equal to the w idth o f the band. T h erefore, instead o f a single x-ray line, the
spectrum consists o f a band o f wavelengths. T h is in fa ct is w h at is observed ex-

F ig. 6-48. Intensity distribution of x-ray transitions for sodium, magnesium, and
aluminum. [Adapted from H. O ’ Bryan and H. Skinner, Phys. Rev. 45, 370 (1934).]
6.8) Radiative transitions in solids 275

A bsorption
B '\

„ I _4_ I I
I o
Ph oto n en ergy

(a)

κ: l i '
-C

h ::

(d)

F ig. 6—19. X-ray absorption transitions in a solid.

perim entally. Figure 6-48 shows the experim ental intensity distributions for the
x-ray transitions to the 2p level for sodium, magnesium, and aluminum. These
intensity distributions are com puted th eoretically by m u ltip lyin g dn/dE, the num­
ber o f electrons per unit volu m e and per unit energy range around the energy E ,
and the p rob a b ility T ( E ) o f a transition from energy E in the band into the low er
energy level. T h a t is,

I ( E ) ~ (d n / d E ) X T ( E ) .

W e have already considered the q u a n tity dn/dE in Section 6.4 and w e can com­
pute T ( E ) according to quantum -m echanical m ethods (see Section 2.11). A sharp
drop o f the intensity ob viou sly occurs for E ~ €*■· In fact, th e energy spread
shown in the graphs o f Fig. 6-48 is o f the same order o f m agnitude as the values o f
« f given in T a b le 6-1. T h e peaks shown b y m agnesium and aluminum are due to
the contribution o f the electrons in the 3p band, while in sodium all electrons are
within the 3s-band.
L e t us now consider the case o f absorption. F igu re 6-49 indicates some typ ica l
situations. In (a ) w e h ave a conductor w ith the upperm ost band B p artially filled
and separated b y an energy gap from the e m p ty band B '. E lectrons in B can be
excited in to nearby e m p ty states in the same band when th ey absorb photons
w ith energies from zero up to the energy required to reach the top o f the band.
T h e other photons that can be absorbed are those that take an electron from B
into B '. T h erefo re the absorption spectrum has the shape shown in Fig. 6 -4 9 (a ),
w ith a gap for the energy region at which no photons can be absorbed. I f the
bands B and B ' overlap, as in F ig. 6 -4 9 (b ), no energy gap exists and a contin­
uous absorption spectrum results. In the case o f an insulator (F ig . 6 -4 9 (c )), only
transitions from the valence band B into th e conduction band B ' arc possible.
276 Solids (6.8

T h erefore, to induce transitions, the photons m ust have a m inim um energy o f a

few eV . T h e resulting absorption spectrum is as shown in Fig. 6 -4 9 (c ). T h is would
also be the case for semiconductors, except th at due to the smallness of their energy
gap, some electrons occupy band B ' ; therefore the absorption spectrum resembles
the situation illustrated for case (b ). La ttice defects, m ainly im purities, have im ­
p ortan t consequences. T h e y introduce new energy levels, which m ay fall in the
energy gap (F ig . 6 - 4 9 (d )). E lectron transitions into these energy levels allow
absorption o f photons o f much low er energies than needed to go from B to B ' ,
and the absorption spectrum is as shown. ■**
Photons in the visible region o f the electrom agnetic spectrum have energies in
the range 1.6 e V up to 3.2 eV. A solid is transparent or opaque depending on its
absorption properties in th at energy range. F o r exam ple, conductors and semi­
conductors are all opaque, since they have absorption curves sim ilar to th at given
in F ig. 6 -4 9 (b ). Pure insulators are transparent if E 0 in F ig. 6 -4 9 (c ) is larger
than about 3.2 eV. B ut if, as a result o f the im purities, the peaks E i in Fig. 6—49(d)
fall in the visible region, the insulator is colored (o r even opaque). F or this reason
these im purities are also called color centers or F-centers (fro m the G erm an farben:
color). F or exam ple, pure corundum ( A I 2O 3) should be transparent, but ruby
(w h ich is A l 2O 3 w ith a small chromium im p u rity) shows a strong red color. Th is
is because the chromium atom s induce a strong absorption in the green region o f
the spectrum, resulting in a red color o f the solid when it is illum inated w ith
w h ite light.
An oth ei im portant rad iative p rop erty o f solids is luminescence. In general, when
the electrons in atoms, molecules, or solids are excited by some means (e.g., absorp­
tion o f radiation or electronic bom bardm ent), there are several processes which
com pete to bring about deexcitation (e.g., ra d iative transitions and inelastic
collisions). In some instances the favored process is rad iative transition and the
substance glow s when it is illum inated w ith radiation o f the proper w avelength,
or is excited by some other means. Substances havin g this p ro p erty are called
luminescent. Lum inescence in solids is closely related to im purities and lattice
defects. F igu re 6-50 illustrates some processes th at tak e place in luminescent
solids. W hen an electron is rem oved from the valence band into the conduction
band, a hole is le ft in the valence band (F ig . 6 -5 0 (a )). In a p erfectly pure and
regular lattice, the electron usually returns to the valence band, although it m ay
tak e some tim e to do so, since both electron and hole have great m ob ility and they
m a y wander in different directions. H ow ever, if the lattice has som e im pu rity
w hich introduces energy levels in the forbidden region, an electron in a low -lyin g
im pu rity level m ay fill the hole in the valence band, w h ile the electron in the
conduction band m ay fall into one o f the (n orm ally e m p ty ) high im pu rity energy
levels, as shown in Fig. 6 -5 0 (b ). These transitions gen erally in v o lve photons o f
small energy which do not fall in the visible region. F in ally, the electron m ay
fall from the high-energy im pu rity le v el to the em p ty low -energy one, em itting
radiation o f less energy (or longer w avelen gth ) than the incident radiation ; this
constitutes the luminescence (F ig . 6 -5 0 (c )). In some instances, instead o f going
through the process shown in F ig. 6 -5 0 (b ), the electron in the conduction band
 References 277

Conduction
Electro
band

Im p u rity · Trap
levels "
—
t ' F'orbidden
S
transition

V alen ce
<>Hole
band

(a) (b) (c) (d) (e)

F ig. 6-50. Mechanism of luminescence.

m ay fall into an energy le v el called a trap, from which a rad iative transition to the
ground-state im pu rity energy level is forbidden (F ig . 6 - 5 0 (d )). In such a case,
the electron is in a state sim ilar to an atom or a m olecule in a m etastable state;
the trapped electron must w ait until, b y som e mechanism, it is returned to the
conduction band, after which it follow s steps (b ) and (c ), as shown in Fig. 6 -5 0 (e).
D ue to the tim e d elay in vo lved , which m ay am ount to m any seconds, the process
is called phosphorescence. These substances are th erefore called phosphors. One
such substance is zinc sulfide. Phosphorescent m aterials are used in the screen o f
cathode-ray and T V tubes, as well as in scintillation detectors which are used to
d etect 7-rays. A phosphor w id ely used in scintillation detectors is K a I activated
w ith T l.

Referenepn

1. “ M aterials,” Sci. Am., September 1967, the entire issue

2. “ Modern Study of Solids,” J. Patterson, Am. J . Phys. 32, 269 (1964)
3. “ Quantum Physics in America Between the Wars,” J. Slater, Physics Today,
January 1968, page 43
4. “ The Structure of Crystal Surfaces," L. Germer, Sci. Am., March 1965, page 32
5. “ Resource Letter SC R - 1 on Semiconductors,” P. Handler, Am. J. Phys. 32, 329 (1964)
6. "Energy Propagation in a Finite Lattice,” W . Band and A. Bhatti, Am. J. Phys.
33, 930 (1965)
7. Introduction to Semiconductor Physics, R. Adler and R. Longini. N ew Y ork: John
W iley, 1963
8. Elementary Solid State Physics, C. Ivittel. N ew Y ork: John Wiley, 1962
9. Structure of Matter, W. Finkelnburg. New Y ork : Academic Press, 1964, Chapter 7
10. Quantum Theory of Matter, J. Slater. New Y ork: M cGraw-Hill,1951, Chapters 10, 12,
13 and 14
11. The Feynman Lectures on Physics, Volume I I, R. Feynman, R. Leighton, and M.
Sands. Reading, Mass.: Addison-Wesley, 1963, Chapter 30; Volume I I I , Chapters
13 and 14
 Problems '279

6.14 Estimate the Pauli paramagnetic

susceptibility of sodium. Compare with
the experimental value of the magnetic
susceptibility of sodium.
6.15 It can be shown that the boundaries
of the Brillouin zones in a two-dimensional
square lattice of side a are given by the
values of kx and k.„ satisfying the equation

·> ·>
n ik x + n2ku = ir(nj - f n2)/a,

where n\ and no are positive or negative

integers. Plot the boundaries of the Brii-
louin zones, using kx and ku as coordinates.
T ry to visualize the energy surface if the
energy is plotted on an axis perpendicular
to the kx-k„ plane. Note incidentally that
the above equation reduces to Eq. (6.21)
for a linear lattice. (H int: Make all possible
combinations of ni and no equal to 0. ± 1 ,
± 2 , . . . and plot the resulting equations.]
6.16 Using a procedure similar to that of
Example 6.4, show that the average energy
of an electron described by the wave func­
tion ip = eikxu (x ) is
Kave = P2k / 2 m + {hk/m)pu,MX + Λ’,,.,,νο,
where was defined in Example 6.4 and
= J u (“ 2m d x l+ Λ " ω ) Wdx'
Figure 6—51
the result. |H int: Neglect terms involving
two φ-functions if they are more than one
cell apart.]
6.19 Suppose that an electron moves on
a circular path along which there are
N ions equally spaced the distance a
(Fig. 6-51). (a) Using wave functions of
the Bloch type, given by Eq. (6.26), show
that the possible values of k are given by
k = 2its/Ea, where s = 0, I, 2, . . . ,.
N — I. (b) A p ]ily this result, combined
with Eq. (6.28), to the 7r-electrons in ben­
zene (Fig. 5-28) to show that the possible
energy levels are
E1
u — a — 2/3, E m — a — 0,
E m — a + β, and E m — a + 20,

where the second and third levels are

Analyze the meaning of each term, \llint:
Look at Table 2-4 for the operator cor­
responding to the energy.)
6.17 The energy of an electron in an an­
isotropic crystal may be expressed by
E — Oiikx -{- <x2k$ -f- auk?, where kXt kv,
and kx are the components of the wave
number vector /.· along the principal axes.
Find the effective mass along each of the
coordinate axes and the equations of
motion.
6.18 Applying the wave function de­
scribed in Eq. (6.26) in the equation for
average energy, show that Eq. (6.28) is
doubly degenerate (the constants E m, a,
and β were introduced in Example 6.6).
6.20 Using the results of Problem 6.19,
(a) show that the energy of the --electrons
in benzene is 6(E m — a ) — 80 for the
ground state, and that the first excited
states are 0, ‘20, and 30 above the ground
state, (b) The first t wo excited states of
benzene correspond to 8.8 eV and 4.9 eV.
From an analysis of the observed energy
levels of benzene, verify that 0 is approxi­
mately 2 eV. On the basis of this informa­
tion, state whether benzene is a colored
substance.
278 Solids
P ro b lv m H
6.1 Show that the number of carbon-
carbon bonds in diamond is twice the num­
ber of carbon atoms (see Fig. 6-1). The
energy required to dissociate one mole of
diamond is 170 kcal. Determine the energy
per bond and express it in eV. Compare
this energy with the energy per bond in sp3
compounds.
6.2 The Madelung constant for the cubic
ZnS structure is 1.638. Calculate the bind­
ing energies for ZnS1for which ro = 2.35 A 1
and CuCll which has the same structure
for which ro = 2.34 A. The experimental
values are 37.9 eV/molecule for ZnS and
9.81 eV/molecule for CuCl.
6.3 Calculate the binding energy of CsCl1
for which ro = 3.56 A. Compare with its
experimental value of 6.72 eV/molecule.
6.4 The bulk modulus of a solid is defined
as K = — ( I / V )(d V / d p ). W h enth een ergy
is only a function of the volume, the above
definition is equivalent to κ = V (d 2U /dV2).
Show that for an ionic crystal,
(n — I ) « V
K = ------------4 ’ energy given in Table 6-1.
187γ«ο R o
Compute the bulk modulus for N aC l1 as­
suming that n = 9. Compare with the
experimental value of 4.2 X IO11 N m -2 .
6.5 Sound velocities in solids arc of the
order of magnitude of 3 X IO3 m s -1 .
Interatomic distances in solids are of the
order of magnitude of 3 X IO-10 m. Esti­
mate the order of magnitude of the cutoff
frequency, assuming a linear lattice.
6.6 Show that for small values of ka, the
two values of ω given by Eq. (6.7) can be
approximated by
6.7 Show that for k = tr/2a, the two
values of ω given by Eq. (6.7) are
ω2 = 20/M i and ω2 = 20/M 2.
6.8 In most diatomic ionic crystals, res­
onance absorption of electromagnetic radi­
ation falls in the infrared (wavelength
about IO-4 m). The interatomic distance
is of the order of 2 X IO-10 m. Estimate
the erro. made when Eq. (6.8) is used to
obtain the resonance absorption frequency
of infrared radiation by the crystal lattice.
Assume that M i and M 2 are the masses of
sodium and chlorine atoms, respectively.
6.9 Using the frequency of maximum
absorption from the absorption curve of
NaCl given in Fig. 6-3, compute the clas­
tic constant 0 of Eq. (6.8). Calculate the
cutoff frequencies for both the acoustical
and optical branches of oscillation.
6.10 The interatomic distance in most
metals is of the order of 4 X IO-10 m.
Estimate the width of the conduction
band. Compare with values of the Fermi
6.11 Calculate the number no of elec­
trons per unit volume in the conduction
band of lithium, copper, and aluminum by
using the Fermi energy values listed in
Table 6-1. Compare your results with the
number of valence electrons per unit
volume for these atoms.
6.12 Estimate the width of a band in
metallic sodium, using Eq. (6.14) and an
equilibrium distance between ions of
3.67 X IO-10 m. Compare your estimate
with Fig. 6-35.
6.13 Sodium has a density of 9.7 X
IO2 kg m -3 . Assuming that each atom con­
tributes one electron to the conduction
band, determine the Fermi energy for so­
dium. Repeat for calcium, assuming two
electrons per atom are contributed to the
conduction band.
280 Solids
F ig u re 6—52
6.21 Assuming that the energy of an elec­
tron in a band is given by Eq. (6.28), (a)
find the value of k at which the velocity of
an electron Ls maximum, and (b) obtain an
expression for m* as a function of k.
6.22 Plot the velocity and acceleration,
as a function of k, of an electron in the
third Brillouin zone whose energy is given
by Eq. (6.28).
6.23 Estimate the radius of the ls-electron
orbit in sodium (Z = I I ) . Compare this
value with the equilibrium distance be­
tween sodium ions and decide whether
such electrons are affected in the metal.
6.24 When an impurity atom is embedded
in a semiconductor, we may assume that
the energy levels of the impurity atoms
are modified. Verify that if E ll0t is the
ionization energy of the isolated impurity
atom, its ionization energy when embedded
in the semiconductor is E ll8C = («ο Λ ) 2E ll8t,
where e is the electrical perm ittivity of the
semiconductor. Compute the ionization
energies of phosphorus (P ), arsenic (As),
and antimony (Sb), which are donor im­
purities, when they are embedded in
silicon (Si) (e/eo = 11.7) and in germa­
nium (Ge) (ί/ίο = 15.8). Compare with ex­
perimental results. IH in t: Recall Eqs. (3.4)
and (3.5) and note that in Rydberg's
constant we should replace eo by e when
the atom is embedded in a material.]
6.25 B y reference to Problem 6.24, ana­
lyze what happens to the size of the elec­
tronic orbits when an impurity atom is
embedded in a semiconductor. A t what
concentration of antimony embedded in
germanium will appreciable overlapping
between the orbits of the outer electrons
of adjacent antimony atoms occur?
6.26 A copper wire with a cross section of
10~a m2 carries an electric current of
1.5 A. Assuming that there are 5 X IO2s
conduction electrons per m3, determine
the current density and the electron drift
velocity.
6.27 A t room temperature the conduc­
tivity of silver is 6.14 X 107Ω-1 m -1 . The
number of conduction electrons is approxi­
mately 6 X IO2s m -3 . Estimate the relax­
ation time t, the Fermi velocity, and the
macroscopic scattering cross section 2,.
Also find the electron mean free path,
defined as I, = 1/2,.
6.28 Estimate the conductivity at room
temperature of NaCl which contains I ppm
(part per million) of divalent cation im­
purities.
6.29 A cubic crystal contains a substitu­
tional impurity in a concentration of 0.1%

(considered normal for “ chemically pure”
materials). Compute the average distance
between impurity atoms, measured in
units of the interatomic distance.
6.30 Very pure germanium used in manu­
facturing semiconductor devices contains
only one part in IO9 of impurities which
affect the electrical conductivity. What
is the average distance between impurities?
6.31 When a metallic ribbon, carrying a
current I , is placed in a magnetic field
perpendicular to the ribbon, a potential
difference appears between opposite points
on the edges of the ribbon (Fig. 6-52).
This is called the Hall effect. Show by
referring to the figure that the direction
of the potential drop across the ribbon
depends on the sign of the charge of the
particles carrying the current. I f 8 is the
electric field set up by the charges accu­
mulated along the edges when equilibrium
is established and (B is the magnetic field,
show that R h = S/j'ffi = I /nq, where j is
the current density, n the number of car­
riers per unit volume, and q their charge.
The quantity R h is called the Hall co­
Problems 281
efficient. [Note: In the figure F is the force
exerted by the magnetic field on the charge
carriers.]
6.32 Referring to Problem 6.31, show that
a line joining two points at the same
potential on opposite sides of the ribbon
makes an angle with the direction of the
current given by tan Θ = ntj/a(R, where a
is the electrical conductivity of the ribbon.
6.33 I f each atom in metallic gold (density
19.3 X IO3 kg m -3) contributes one elec­
tron to the current, what is the Hall coeffi­
cient for this metal? A thin gold strip
carries a current density of IO7 A m -2 in
a transverse magnetic field of IO-2 T .
What is the angular displacement of equi-
potential lines, given that the conductivity
of gold is 5 X IO7 Ω -1 m - 1 ? [H in t: See
Problems 6.31 and 6.32.]
6.34 In NaCl, the F-center energy level
is 2.65 eV below the conduction band.
What wavelength does it absorb? What
color is NaCl containing /'’-centers?
6.35 The energy gap in germanium is
about 0.75 eV. A t what wavelength does
germanium begin to absorb light?
 7
NUCLEAR STRUCTURE

7.1
7.2 Isotopes, Isolones, and Isobars
7.3 The A tom ic Mass U n it
7Λ Properties o f the Nucleus
7.5 Nuclear Binding Energy
7.6 Nuclear Forces
7.7 The Ground Stale o f the Deuleron
7.8 N e u lron -P rolon Scattering at Loiv Energies
7.9 T h e S h e llM o d e l
7.10 Nuclear Radiative Transitions
7.2) Isotopes, isolones, and isobars '283

7.1 Introiliirtion

T o com plete our discussion o f the structure o f atoms, w e must now look into the
nucleus o f the atom. T h e atom ic nucleus is a cluster o f protons and neutrons
occupying a small region at the center o f the atom , w ith a diam eter o f the order
of IO-14 m ; that is, about one ten-thousandth the diam eter o f the atom . Protons
and neutrons are designated b y the com m on name o f nucleons. B o th particles
have spin £ and ob ey the exclusion principle.
W hen w e com pare the structure o f the nucleus w ith th at o f the atom, several
new features strike us. In the first place, all the particles th at m ake up the nucleus
have practically the sam e mass, w h ile in atom s the electrons are v e ry liglrt
compared w ith the nucleus. F o r th a t reason w e assumed (in C h ap ter 3) th a t the
electrons m oved around a nucleus which rem ained fixed in an inertial frame.
Therefore w e cannot speak o f a central dom inant force which acts on the particles
composing the nucleus and which is produced by a b od y at the center o f the nucleus;
rather w e must im agine all particles m ovin g under their m utual interactions. A t
most, as a useful sim plification, w e m ay think o f a sort o f average field o f force;
i.e., we m ay im agine each p article m ovin g under a force resulting from averaging
the forces produced by the other particles during their m otion. In a first approxi­
mation, w e m ay consider this force as central. In a second approxim ation, addi­
tional noncentral forces m ay be required. T h is sim plified approach has proved
very useful in analyzing nuclear structure.
In the second place, in an atom the electrons possess n e gative charge and
the nucleus has p ositive charge, and it is possible to explain electronic m otion in
terms o f electrom agnetic interactions between the electrons and the nucleus.
But a nucleus is composed o f protons, w ith p ositive charge, and neutrons,
with no charge at all. T h erefo re w e cannot attrib u te the stab ility o f the nucleus
to electric attraction. On the contrary, it seems likely that the electric repulsion
between the protons would send the nucleus flyin g apart. T h e m ere fact th at
nuclei composed o f protons and neutrons exist is a clear indication o f the presence
of another interaction besides the electrom agnetic interaction, an interaction which
is not directly related to electric charges and which is much stronger than electro­
magnetic interaction. T h is interaction is called nuclear or strong interaction. Our
knowledge o f the nuclear interaction is still incom plete, but at least w e do know
some o f its m ore im portant characteristics.

7 .2 I sot o p r s. Isoton rs. anil Iso b a rs

VVe id entify a nucleus b y the num ber o f protons it has, or its atomic number Z 1 and
by the total number o f particles or nucleons it has, called its mass number .1. Thus
the number o f neutrons is IV = Λ — Z . T h e term nuclide has been introduced to
designate, in a generic w ay, all nuclei havin g the same Z and N 1 and hence also the
same A . In other words, in the same w a y that all atoms w ith the same Z belong
to the same element, all nuclei o f the same com position (th e same Z and N ) belong
to the same nuclide. A nuclide is designated by the sym bol o f the chem ical ele­
284 Nuclear structure (7.2

m ent to w hich it belongs, according to the valu e o f Z , w ith a superscript to the

le ft indicating th e valu e o f the mass number, such as 12C, 23N a 1 107A g 1 238U.
Som etim es it is convenient to w rite the atom ic number Z exp licitly, in w hich case
a subscript to the le ft is added 1I-C1 ??Na, 10^ A g 1 2|8U.
N u clea r force is not so discrim inating as to require a fixed ratio in the number
o f protons and neutrons th at can coexist in a nucleus. T h e re can be considerable
flexib ility in th eir grouping. A lth ou gh there are on ly 92 natural chemical elements
(11 m ore have been produced a rtificia lly), there are in the order o f 1440 different
known nuclides, som e 340 existing in nature and about 1100 produced in the
laboratory. Som e o f the nuclides (abou t 280 o f them ) are stable, but a large num­
ber are unstable or radioactive. F igu re 7-1 indicates m ost o f the known nuclides.
T h e stable nuclei are indicated b y the black squares and the unstable or radio­
a ctive nuclei b y the other symbols.
W e m ay observe from the figure that, in light nuclei, neutrons and protons tend
to be in equal numbers ( N «= Z ) , which indicates th e independence o f the nuclear
interaction from the electric charge. H ow ever, in h eavier nuclei, the number of
neutrons exceeds th at o f protons (A r > Z ). T h e re must be an excess o f neutrons
to produce a stabilizing effect (through nuclear in teractio n s); these extra neutrons
balance the disrupting effect o f the coulomb repulsion between protons.
Because o f the great v a riety o f nuclides, w e shall classify them in three cate­
gories: isotopes, isotones and isobars.
Isotopes are nuclides having the same number o f protons but different numbers
o f neutrons; th erefore th ey have the same atom ic number Z but different neutron
number N and d ifferent mass number A . Since a chemical elem ent is identified
b y its atom ic number Z , all isotopes corresponding to a given value o f Z belong to
the same element. F o r example, JhI and 2H are isotopes o f hydrogen. B oth
nuclei h ave Z = I, but JhI has N = 0 and 2H has N = I. Isotopes fall along
vertical lines in F ig. 7-1.
In to n e s are nuclides havin g the same number o f neutrons N but a different
atom ic number Z (o r number o f protons), and therefore also a different mass
number A . Isotones having a given valu e o f N ob viou sly do not all correspond to
the same chemical element. F o r example, 'jjC and 13N are isotones. B oth nuclei
h ave N = 7, but carbon has Z = 6 and nitrogen Z = 7. Isotones fall along hori­
zontal lines in F ig. 7-1.
F in ally, isobars are nuclides which have the same to ta l number o f nucleons (o r
same mass number .4), but which differ in atom ic number Z and also in neutron
num ber N . F o r exam ple, 1^C and ’ y N are isobars, since both h ave A = 14.
Isobars fall along the 45° lines shown in Fig. 7-1.
Som e chem ical elements occur in nature w ith on ly one v a rie ty o f nucleus or
isotope. A n exam ple is 1^F. Others have several natural isotopes, such as tin
which has ten, and carbon which has three: 1I C 1 'jjC , and 1JjC. In addition, four
m ore isotopes o f carbon h a ve been produced artificially. O f all carbon existing in
nature, 98.89% is in the form o f 'l C . T h e natural isotopic com position o f any
given chemical element is fa irly uniform throughout the world.
 ■ Stable nuclei
ο β~ emitters
+ β+ emitters (or electron capture)
® β+. β~ emitters (or electron capture)
λ I «-emitters (with β~, β or electron capture)·^
□ ja-emitters (pure or 0-stable)
N
number,
Neutron

Z = N for nuclides lying on this line

Proton number, Z

'8· 7-1. Stable and radioactive nuclides. The 45° lines are lines of equal mass number .4
286 Nuclear structure (7 A

T h e analysis o f the properties o f isotopes, isotones, and isobars is im portant in

th at it discloses several features o f nuclear structure. Such studies help us, for
exam ple, to pred ict w h at w ill happen to the stab ility o f a nucleus when an extra
neutron or p roton is added to it, or to decide which configurations o f neutrons and
protons w ill be the m ost stable.

7.11 Tho Λ /o n iir M a s s T a il

W h en w e deal w ith certain properties o f nuclei, w e do not need to express the
masses o f th e nuclei in kilograms. R ath er, in m any instances, it is m ore conve­
nient to use a special unit called the atomic mass unit (am u ), which is equal to
on e-tw elfth o f the mass o f the 12C atom . (N o t e th a t w e say atom and not nucleus,
and thus this mass unit includes the orb iting electrons.) T h a t is,

• I amu = J12 x mass o f one 12C atom.

In term s o f kilogram s, t he valu e o f one amu is

I am u = 1.0604 X IO-2 7 kg. (7.1)

One m ole o f any substance is b y definition a mass equal to IO- 3 A f kg (o r A/ g )

where M is nu m erically equal to the atom ic (o r m olecular) mass o f the substance
expressed in amu. A v o g a d ro ’s constant N a is the number o f atom s (o r molecules)
in one m ole o f any substance. Since the mass o f one atom (o r m olecule) is equal
to 1.6604 X 10-2 7 ilf kg, we conclude th at

- Lceolxw-W - 00225* 10” “ k~'·

Since N a is independent o f M , the num ber o f atom s (o r m olecules) in one m ole is
the same for all substances.
T h e masses g iven in the chart o f nuclides (see rear insert) are expressed in amu.
T h e atomic mass o f an elem ent is the average mass based on the natural isotopic
com bination. T h u s the atom ic mass o f carbon is not 12.00000 amu but 12.0111.5
amu, due to the presence in nature o f different carbon isotopes.
B v using the relation E = me2, w e m a y express the energy equ ivalen t o f one
amu interm s o f joules or electron volts. W e lea ve the student to v e r ify th at

I amu = 9.31478 X IO8 e V = 931.478 M e V ,

or about one b illion eV ( I G e V ).

7 .1 V ro p v r tio s o f Iho X nolon s

T o obtain a clue about the nature o f the forces holding protons and neutrons
togeth er in a nucleus, scientists have analyzed several physical properties o f nu­
clei besides charge and mass. W e shall now review som e o f these properties.
TA) Properties of the nucleus 287

(a) (Ij)

F ig . 7-2. (a) ^iuclear density and (I j) charge density as functions of the radial distance.
[From B. I). Hahn, I). G. Ravenhall1 and K. Hofstadter, Phys. Rev. 101, 1131 (1956)1

(I) S iz e . I f w e assume that a nucleus is spherical, w e m ay express its size in

terms o f its radius li. W e must, how ever, use this concept o f nuclear radius w ith
some care. W e must n ot picture the nucleus as a billiard ball w ith a well-defined
surface. T h e valu e o f I he radius depends on w hich nuclear p ro p erty w e choose t o
determ ine the radius. T h e density o f nuclear m atter varies w ith the distance from
the center o f the nucleus, as indicated in Fig. 7 -2 (a ). T h e density is approxim ately
constant for a considerable distance from the center, and then gradually decreases
down to zero near the surface o f the nucleus. T h e nuclear radius I t m ay then be
defined as the distance from the center o f the nucleus at w hich the nuclear density
has been reduced b y one-half. W e can obtain this radius It, for example, by
measuring the dilTcrcncc in energy due to the coulom b interaction between adjacent
isobars (i.e., between isobaric nuclei that differ in Z by one unit) or by analyzing
different typ es o f nuclear processes, such as the scattering o f fast neutrons Iiy
nuclei. T h e experim ental result is that the nuclear radius is proportional to .-11/3,
where A is the mass number o f the nucleus. T h a t is,

It = r 0, t » ' 3, (7.2)

where r 0 is a constant, the same for all nuclei. Its accepted value is

r0 = 1.4 X 10“ 15 m.

I t is also possible to determ ine the charge distribution inside a nucleus and from
it estimate the nuclear radius. Iixperim ents w ith v e r y fast electrons and muons
suggest a charge distribution as indicated in Fig. 7 -2 (b ). T h e radius o f the charge
distribution is sm aller than that o f the mass distribution, corresponding to a
value
r0 « 1.2 X IO- 1 5 m.
288 Nuclear structure (7.4

Som e nuclei depart substantially from the spherical shape and m ust be assumed
to be ellipsoidal or even pear-shaped.
Since the volum e o f a sphere is A irR 3/3, w e conclude from E q. (7.2) th at the
nuclear volu m e is

V = 4w rgA/3 = 1.12 X 10-4 5 -l m - 3 .

T h a t is, the volume o f a nucleus is proportional to the number o f nucleons A . T h is

suggests that the nucleons are m aintained at fixed average distances, independent
o f the number o f particles, so that th e volu m e per nucleon is a constant qu antity,
the same for all nuclei. Λ sim ilar situation exists for molecules in a liquid or in a
solid.
A n oth er conclusion is that nuclear matter has a constant density. T h is m ay be
seen as follow s: T h e mass o f a nucleus o f mass number .4 is approxim ately

M = 1.66 X IO-2 7 A kg.

T h erefore the average density o f nuclear m atter is

o - — = 1 6 6 x 10~27Λ kg 18 3
P V 1.12 X IO-4 5 A m 3 1 4 j X 10 K6 m >

which is independent o f .4. T h is density is about IO 15 tim es greater than the

density o f m atter in bulk, and gives us an idea o f the degree o f compactness o f
the nucleons in a nucleus. I t also shows th at m atter in bulk is essentially em pty,
since m ost o f the mass is concentrated in the nuclei.

(2 ) A n g u la r m o m e n t u m . T h e resultant angular mom entum o f a nucleus is

called (fo r historical reasons) the nuclear spin. I t is designated by I. B oth protons
and neutrons, like electrons, have spin In addition, protons and neutrons
possess orbital angular m om entum associated w ith their m otion in the nucleus.
T h e resultant nuclear angular m om entum (o r spin) is obtained by com bining, in
a proper w ay, the orbital angular m om enta and the spins o f the nucleons com ­
posing the nucleus. T h e nuclear spin is designated b y a quantum number I such
th a t the m agnitude o f the nuclear spin is h\/7(7 + I ). T h e com ponent o f the
nuclear spin in a g ive n direction is given b y m/ft, where m/ = ± 7 , ± ( 7 — I ), . . . ,
or 0, depending on w hether 7 is a half-integer or an integer. T h erefore there
are 27 + I possible orientations o f the nuclear spin. A s explained in Section 3-4,
these same rules are va lid for all angular m om enta in quantum mechanics. E x­
p erim entally the values o f I are integers (if .4 is even ) or half-integers (if A is odd)
ranging from zero, as in 4H e and 12C, up to 7, as in 176Lu. T a b le 7-1 presents
some nuclear spins. I t has been noted that p ractically all even-even nuclei (i.e.,
nuclei that have an even number o f neutrons and protons) have 7 = 0, which
indicates th at identical nucleons tend to pair th eir angular m om enta in opposite
directions. T h is is called the pa irin g effect. E ven -od d nuclei (i.e., nuclei that have
 Properties of the nucleus 289

an odd number o f either protons or neutrons) all have half-integral angular mo­
menta, and it is reasonable to assume th at the nuclear spin coincides w ith the
angular m om entum o f the last or unpaired nucleon, a result which seems to hold
in m any cases. Odd-odd nuclei have tw o unpaired nucleons (one neutron and one
proton) and the experim ental results are a little m ore difficult to predict, but
their angular m om enta are integers, as one would expect, since there is an even
total number o f particles. A n y theory o f nuclear forces, to be satisfactory, must
account for the experim ental values o f I.

(3) M a g n e t ic d ip o le m o m e n t . W e m ay recall (see Section 3.0) that a m oving

charge possesses an orbital m agnetic dipole m om ent M t, which is proportional to
its orbital angular m om entum L and which is g iven by

M l = (q / 2 m )L .

F o r the case o f protons, the charge is q = e, and therefore

M l = (e/2mp) L . (7.3)

O bviously neutrons have no charge and do not have an orbital m agnetic dipole
moment. T h e com ponent o f the m agnetic mom ent along the Z-axis is

M l ., = (c /2 mp)L 2 = {ch/2mv)m i = μ κιη t,

where the constant

μκ = eh/2mp = 5.0504 X IO-27 J T -1 (7.4)

is called a nuclear magneton.

I f the particle has spin S, it m ay have an additional spin m agnetic dipole m om ent
given by
Ms = gs {e/2mp) S or M s ., = g.sp\ms , (7.5)

where gs is a constant characteristic o f the particle, called the spin gyromagnetic

ratio.* T h e value for the proton is gs .p = +5.5855, indicating that M s is parallel
to S (as corresponds to a positive charge). I t has been observed th at the neutron,
although it has no electric charge, has a spin m agnetic m om ent corresponding to
gs.n = — 3.8263. T h e negative sign indicates th at M s is antiparallel to S, as cor­
responds to a n egative charge. These results suggest th at the proton and the
neutron have a com plex structure which w e have not y e t been able to determ ine
exactly.
W e can obtain the resultant m agnetic dipole m om ent o f a nucleus b y combining,
in a proper w a y , the m agnetic dipole mom ents o f all the nucleons. O bviously, the
resultant m agnetic dipole m om ent must be related to the nuclear spin I . The

* Recall that for the electron gs = —2.0 (see Section 3.7).

290 Nuclear structure (7.4

relation, which is an extension o f E q . (7.5), is

where <ji is the nuclear gyrom agnetic ratio. T h e com ponent o f the resultant m ag­
netic dipole mom ent of a nucleus along a given direction m ay be expressed b y
Ms = f f / ( c / 2 m , o r since I 2 — m jh ,

M t = Mng m i - (7.6)

N uclear m agnetic m om ents are listed as m ultiples o f μ χ , and for m j I. That

is, μ = M 2/μ s — (Ji I■ A ccord in gly th e m agnetic m om ents o f the proton and
neutron (w ith I = A) are μρ = +2.7927 nm and μ χ = — 1.9131 nm. T a b le 7-1
gives som e valu es o f μ. T o be satisfactory, a th eory o f nuclear interactions must
account fo r the observed values o f μ or <//.

(4 ) E le c t r ic q u a d r u p o le m o m e n t . rI he electric quadrupole m om ent of a

charge distribution rela tive to a given direction designated the Z-axis is defined b y
Q 1 = 2,-qe(3zz — r f ) . In th e nuclear case on ly the protons con trib u te to the
electric quadrupole and, since qt = e, w e get Q ' = c ]r ,,(3 z 2 — r p). N o rm a lly the
nuclear quadrupole is defined as Q = Q '/e. O b viou sly th e valu e o f Q depends on
th e direction o f the Z-axis. B y convention, the Z-axis is chosen to be as parallel
as possible to th e nuclear spin I , so that m j = I. H en ce the nuclear electric quad­
rupole m om en t is defined by

Q = Σ ρ (3 z l - r X (7.7)

In the M K S C system , Q is expressed in m 2. Som etim es a unit called the bam is

used; one barn is equal to IO-28 m 2. I f the protons arc distributed w ith spherical
sym m etry, Q = O; thus the valu e o f Q is a good indication o f the degree to which
a nucleus departs from the spherical shape. I f Q is positive, th e nucleus must
resem ble a prolate ellipsoid, and if Q is negative, the nucleus must look like an
ob late ellipsoid (F ig . 7 -3 ). I t can be shown th eo retically that nuclei w ith 7 = 0

F ig. 7-3. Charge distribution, symmetric with respect to the Z-axis: (a) sphere, (b)
prolate ellipsoid, (c) oblate ellipsoid.
 Properties o f Som e N u clid es

Magnetic
Atomic mass,
*U C Spin dipole
amu
moment, nm

oi 1.008665 -1.9131
I
1.007825 2.7927
‘2
I 2.014102 0.8574
3
3.016989 -2.1275
3
3.016050 2.9789
I7 4.002603 0
3 7.016004 3.2563
1I 12.00000 0
'I' 13.00335 0.7024
14
7 14.00307 0.4036
!5
15.00011 -0.2831
‘ S' 15.99492 0
16.99913 -1.8937
21
10 20.99395 -0.6618
27
Ι3> 26.98153 3.6414
Π* 34.96885 0.8218
20* 39.96260 0
20* 42.95878 5 -1.3172
56-
2«; 55.9349 0 1.06
26 56.9354 i 0.0905
60,
27* 59.9338 5 3.8100
63,
20* 62.9296 i 2.2260
7-.
35 78.9183 2.1060
«S»
3S‘ 87.0564 0
93
92.9064 6.1670
103
45 102.9048 0
114I
48’ 113.9034 0
127
53 126.9045 2.8080
154.9277 -0.2700
17ft
71 174.9409 2.2300
I7f.
71 175.9427 3.1800
177
176.9439 2.2400
I KO
179.9468 0
I Kft
75 184.9501 3.1716
20K
82 205.9892 0
209
93 208.9S04 4.0802
227
S3· 227.0278 1.1
233
92 233.0395 0.54
235
92 235.0439 0.35
23K
92 238.0508 0
241
94 240.4236 -0 .7 3 0
292 Nuclear structure

20 40 60 SO 100 120 140

Odd n iirloon s .V o r A

F ig. 7-4. Electric quadrupole moments for odd--4 nuclei. The ordinate is the unitless
quantity Q /ZR 2, which is a better indicator of the deviation from a spherical shape.

or £ h ave Q = 0, a result confirm ed experim entally. T a b le 7-1 gives the values

o f Q for some nuclei. F igu re 7-4 shows the observed electric quadrupole mom ents
o f a few nuclei. N o te th at some nuclei have abnorm ally large electric quadrupole
m oments, indicating v e ry large deform ations. Again we say' th at a th eo ry of
nuclear interactions, to be satisfactory, must account for the observed values o f Q.
7.5) Nuclear binding energy '293

(5) P a r it y . N uclear states lia v e a certain p a rity, even or odd, depending on the
structure o f the w a v e functions describing the states. Each nuclear w ave func­
tion depends on the w a ve functions corresponding to each o f the nucleons. Thus
the p a rity o f nuclear states is v e ry closely related to the nucleonic motions. H o w ­
ever, this subject is a v e ry com plicated one, on which we shall not elaborate
further at present.

E X A M P L E 7.1. Calculation of the repulsive potential energy clue to coulomb inter­

action among the protons in a nucleus.

S o lu tio n : The electric energy of a homogeneously charged sphere, of total charge Q

and radius R, is

3 Q2
"<cou') ~ 5 -Irrc0R '

Assuming that the Z protons in a nucleus are distributed uniformly, we may adapt this
result by replacing Q by Ze and replacing R by the value given in Eq. (7.2). Therefore
the coulomb energy of a nucleus is

- 3 ^ 2g2 _ 3 / c2 \ Z 2
ii(coui) - ft 5 \ lrre0r0/ . l l/3

Introducing numerical values, we have

/fpcccuD = 9.S7 X IO - 14Z 2.1 - 1' 3 .1 = 0ΧΛ7Ζ-Λ ~ 1/3 M e V . (7.8)

Since the electric charge Ls not spread uniformly over the nuclear volume but is concen­
trated at the protons, we should use Z (Z — I ) instead of Z - because each of the Z-protons
interacts only with the remaining Z I protons. This correction is especially important
for nuclei with small Z, such as helium. For example, for 4H c1 with Z = 2 and .1 = 4,
we have E P{couii = 0.776 M eV (using the corrected formula), and for 2SilTt with Z = 92
and .1 = 238, we have E p(Coui> = 87‘J M eV . We >ec that, because of the Z - term, the
coulomb repulsion energy increases very rapidly with the number of protons. Fnless the
nuclear interaction is strong enough and attractive, the nucleus cannot be stable. We
must compare these electric energies with those of atoms and molecules, which are of the
order of a few electron volts. The reason for the big difference is that the protons in a
nucleus are much more closely packed than electrons in an atom, their separation being
about one hundred-thousandth as much as the average separation of electrons in atoms
or molecules, resulting in an energy roughly 100,000 times greater.

? ..* X u v lv a r H ind in y Iinvrfiy

W e can g et an idea o f the strength o f the nuclear interaction by studying the bind­
ing energy o f nuclei; th a t is, the energy required to separate the nucleons com ­
posing a nucleus. T h e mass o f a nucleus is appreciably less than the sum o f the
masses o f its com ponent nucleons. F or exam ple, in the case o f the deuteron,
W0 = 2.014102 umu. T h e masses o f the proton and the neutron arc

W1, = 1.007825 anni and w„ = 1.008605 antu.

2,9'/ Xurlear structure (7.5

T h c ir sum is Wip -H m n = 2.016490 amu, w hich is larger than wz,j b y the am ount
0.002388 amu. T h e explanation o f this loss o f mass lies in the binding energy o f
the system.
C onsider one proton and one neutron a t rest and sufficiently far apart so that
there is no interaction between them. T h e ir total energy is then the sum o f their
rest masses; th at is,

E = WipC2 + WinC2 = (wip Λ wi,Jc2.

N o w suppose th a t the tw o particles are close enough to form a deutcron nucleus

as a result o f th eir nuclear interaction. L e t us call E p th eir nuclear potential
energy. T h e y are m ovin g about their center o f mass and thus also h a ve som e
kinetic energy E k. T h erefo re th eir total energy is now

E' = (wip - f wi„)c2 + E k - f Ep.

But if the nuclear forces are a ttra c tiv e and the zero o f poten tial energy is chosen
at infinity, E p is negative. A lso, since the deutcron is a stable system, E p must
b e larger than E k in absolute valu e so that E k -T E p is n egative (rem em ber th at
in the case o f th e hydrogen atom, as w e ll as in all bound systems, th e total energy,
excluding the mass energy, is n egative). T h erefo re, E ' is sm aller than E , or in
other words, energy is liberated when the system o f tw o bound nucleons is form ed.
T h e energy liberated is

Eb = E - E 1, (7.9)

w hich is called th e binding energy o f the system . T h is am ount o f energy m ust be

give n back to the deuteron to separate the neutron and the proton. W c can m ore
rea d ily understand these relations if we look a t Fig. 7-5. T h e nuclear binding
energy in the case o f the deuteron is the equ ivalen t o f the ionization energy in the
case o f t he hydrogen atom.
E n ergy a t
in finite separation

E n erg y in
Ixnind state
by = m.ic2

Ep
F ig. 7-3. Binding energy of deuteron.

A n "e ffe c tiv e ” mass o f the n-p system can be defined b y the relation E ' = m,ic2,
resulting in a value for wia sm aller than mp T wt„. T h e binding energy o f the
deuteron is then

Eb = ( » i p T Wi1J c 2 — WiaC2 = (wip T wi„ — wi.Jc2

= 931.48(wip T Win — wia) M cV .
7.5) Nuclear binding energy 295

In th e last expression th e masses must be expressed in amu. Since

»ip + » i „ — wi,i = 0.002388 amu,

th e binding energy o f the deuteron is E t = 2.224 M e V . T h is is therefore the

energy required to separate the proton and the neutron in a deuteron, or the energy
released when a proton and a neutron at rest are com bined to form the deuteron.
C om parin g this energy w ith the equivalent result for hydrogen, whose ionization
(o r binding) energy is o n ly 13.0 eV, w e conclude th at the nuclear interaction is
about IO'1 tim es stronger than electrom agnetic interactions. Incid en tally, no
measurable change in mass is observed in chemical reactions because th e energy
in vo lved in most electrom agnetic processes is rela tiv ely small, o f the order o f a
few eV , equ ivalent to a change in mass o f a few billionths o f mass units per atom.
F o r a nucleus o f mass M composed o f A nucleons, o f w hich Z are protons and
A - Z are neutrons, the binding energy (i.e., the energy required to separate all
nucleons) is
E b= IZn ip + ( A — Z )m „ — M } c 2
= 931.48[Zmp -+- {A - Z )m n - M ) M eV . (7.10)

In the second expression all masses must be expressed in amu.

A good indication o f the stab ility o f a nucleus is the average binding energy
per nucleon, Ei,/A . Its valu e fo r various nuclei is shown in Fig. 7-6. One can see
that it is m axim um for nuclei in the region o f mass number A — CO. Therefore,
if tw o light nuclei are join ed togeth er to form a medium-mass nucleus (a process

F ig. 7-6. Binding energy per nucleon as a function of mass number.

296 Nuclear structure (7.5

called fu s io n ), energy is liberated, and if a h eavy nucleus is d ivid ed into tw o

m edium-mass fragm ents (a process called fission ), energy is also liberated.
T h e fact th at the binding energy per nucleon is practically constant (a b ove
A = 10, the v ariation is on ly 10% ) suggests th at each nucleon interacts on ly
w ith its im m ediate neighbors, independently o f th e total number o f nucleons;
this p rop erty is called saturation. T h is saturation effect is also found in molecules,
in w hich the binding energy o f tw o atom s is practically independent o f the other
atom s in the molecules. T h e same situation occurs in liquids and solids.
A n em pirical expression for the binding energy o f a nucleus was proposed around
1935 b y the G erm an physicist C. V. W eiszacker. A s w e have indicated, the bind­
ing energy per nucleon is approxim ately constant and therefore the total binding
energy o f a nucleus should be proportional to the total number o f nucleons or the
mass number A ; that is, Es = Oi A , where a, is a constant o f proportion ality.
H o w ev e r, the nucleons close to the nuclear surface are less tigh tly bound than
those inside because they have few er neighbors wi th which to interact. T h u s w e
have to correct our first estim ate o f Es by adding a n egative term. Since this is a
surface effect, the new term must be proportional to the square o f the nuclear
radius or, in view o f E q . (7.2), proportional to A 213. Thus w e m ay w rite

Es = U1A - a 2A 213.

N e x t w e must consider the repulsive coulom b energy o f the protons, which also
tends to decrease the binding energy. F ro m E xam ple 7.1 w e conclude that the
coulom b correction must be proportional to Z 2A ~ ' 13. Thus w e m ay w rite

Es - α ι -I — a 2A 213 — a3Z 2A ~ 113.

A n oth er term w hich tends to decrease the binding energy is the kinetic energy o f
the nucleons. A s w e shall see in E xam ple 13.3, the kinetic energy o f the nucleons
is p roportion al to .4 + f (. V — Z ) 2A ~ l . T h e first part, which is proportional to .1,
can be included in the a%A term. T h u s the kinetic energy correction am ounts to
adding a term o f the form — a4( N — Z ) 2A ~ ', so th at

Es = U1A - U2A 213 - O3Z 2A - ' 13 - Ci4(.V - Z ) 2A ~ '. (7.11)

W e can obtain the four constants by fittin g the equation to the experim ental values
o f Es, which w e get b y using E q . (7.10). I f w e choose the constants to fit the
binding energies o f nuclei w ith odd .4 (th a t is, Z od d and Ar even, or the reverse),
we find th at the binding energy o f nuclei w ith .4 even fall system atically on either
side o f the values g iven by E q. (7.11), w ith even -even nuclei havin g a larger bind­
ing energy and odd-odd nuclei having a sm aller binding energy. Thus to obtain
the best fit o f E q. (7.11) fo r all nuclei w ith .4 > 10, we add a corrective term 5,
such that

N A
E ven E ven Even
E ven Odd I
Odd
Odd E ven I
Odd Odd E ven
7.5) Nuclear binding energy 297

T h e origin o f this term is related to the p a irin g energy o f nuclei. T h a t is, as a

result o f the pairing effect m entioned in Section 7.4, the nuclear interaction seems
to depend on the rela tive orientation o f the angular m om enta o f the nucleons;
therefore the binding energy depends on how m any pairs o f nucleons have their
angular m om enta in opposite directions, or are paired. T h is number is rela tiv ely
sm aller in odd-odd nuclei and larger in even-even nuclei, resulting in a larger
binding energy for the latter.
T h e best values o f the constants, expressed in M c V , are

O1 = 15.700, a2 = 17.810, a3 - 0.711,

a4 = 23.702, a5 = 34.

I t is suggested th at the student check the v a lid ity o f E q . (7.11) by ap plyin g it to

several nuclei.
N o te that, from E q. (7.10), w e m ay express the mass o f a nucleus in the form

Al = Zm p + (/I — Z )m „ — Eb/c2
= Zm p + (A - Z ) m n- a\A + a'2A 213 + a'3Z 2A ~ 113
+ a \ (N - Z ) 2A ~ x - S'. (7.12)

T h e values o f the constants appearing in E q. (7.12), when expressed in amu, are

a\ = 1.69 X IO- 2 , a'2 = 1.91 X IO- 2 , o'3 = 7.63 X IO- 4 ,

a’A = 2.54 X IO- 2 , o'j = 3.6 X 10 ~ 2.

E X A M P L E 7.2. Difference in mass of “ mirror” nuclei; i.e., nuclei having the same odd
A but with N and Z interchanged. One pair of mirror nuclei is 2H and 2He. Another pair
is u N a and 22Mg-

Solution: Consider odd-.4 mirror nuclei which differ by one unit in N and in Z, with
one having (N , Z ) and the other (N — I 1Z -j- I). Disregarding the pairing energy term
in Eq. (7.12), since Λ is odd for both nuclei, and noting that N - Z = ± 1 , so that the
kinctic-energy term cancels out, we have

Atz+ 1 — Atz —>'ip — m „ -j- a'3[ ( Z - f- I ) 2 — Z 2JA 1/2

= 7«p - m„ + a3( 2 Z + 1 )A ~ 1/3.

Actually, since mirror nuclei are light nuclei, with low Z , the coulomb term must be used
with Z ( Z — I ) instead of 7 2, as indicated in Example 7.1. Thus

A fz + 1 - AIz = mp - m„ + 2 a ^ r 1/3

= ( - 1 . 3 9 0 + 1.526Z.1-1 ' 3) X IO-3 amu.

W c can use this equation to obtain a3 from the observed value of the masses of the mirror
nuclei; from the measured value of a3, we can obtain the constant ro for the nuclear
radius. I t is suggested that the student apply this formula to the two cases mentioned
above.
298 Xuctear structure (7.6

E X A M P L E 7.3. Calculation of Ihc atomic number of the most stable nucleus for a
given mass number .4.

S o lu tio n : The most stable nucleus with a given mass number .1 is that which has the
maximum value of the binding energy. Thus we have to compute OEb/dZ with Λ con­
stant, and equate it to zero. From the expression for Eb given in Eq. (7.11), and since
N — 7j = .1 — 2Z, we have that

OEb/dZ 2α3Ζ/1_1/3+ 4 α 4(Λ - 2 Z )A ~ 1 = 0,

or, introducing the numerical values of β3 and a4, we have

Z = 2 + 0.0157Λ 2' 3 ‘ (7' 13)

For light nuclei, having small .1, we can neglect the second term in the denominator, and
we have approximately Z « £.1, a result confirmed experimentally. It is suggested that
the student make a plot of Z as a function of .1 up to 240 (go in steps of 20) and compare
with Fig. 7-1.

7.H X u r lv u r Fttrvvtt
L e t us now sum m arize the m ain properties o f nuclear forces, some o f which we
h ave already m entioned.

(I) T h e n u c le a r f o r c e is o f s h o r t ra n g e . Short range means th at the nuclear

force is appreciable on ly when the interactin g particles are v e r y close, at a sepa­
ration o f the order o f 10- l s m or less. A t greater distances the nuclear force is
negligible. W e m ay infer that the nuclear force is o f short range because a t dis­
tances greater than IO-14 m, corresponding to nuclear dimensions, th e interaction
regulating the scattering o f nucleons and the grouping o f atom s into molecules is
electrom agnetic. I f the nuclear force w ere o f long range, the nuclear interaction
between the atom ic nuclei would be fundam ental in discussing m olecular form a­
tion, d om inating the w eaker electrom agnetic forces in the same w ay th at the
electrom agnetic interaction dom inates the even w eaker g ravita tion al interaction
in the form ation o f atom s and molecules.
T h e range o f nuclear forces m ay be determ ined d irectly b y perform ing scattering
experim ents. Suppose, for example, th at w e send a proton against a nucleus. T h e
proton, on approaching the nucleus, is subject both to the electric repulsion and
the nuclear force. I f the nuclear force is o f a range com parable to th at o f the elec­
tric force, the m otion o f the proton, no m atter how close or how distant it is when
it passes the nucleus, would be affected b y both typ es o f force and the angular dis­
tribution o f the scattered protons would d iffer appreciably from the results for pure
electric (o r coulom b) scattering. On the other hand, if the range of the nuclear force
is small, those protons passing at a distance from the nucleus greater than the range
o f the nuclear force essentially experience on ly a pure electric force. O nly those
protons w ith enough kinetic energy to overcom e the coulom b repulsion and pass
close to the nucleus are affected b y the nuclear force, and their scattering is differen t
7.6) Nuclear forces 299

from pure coulom b scattering. T h is la tter case is the situation observed experi­
m entally, confirm ing the short range o f the nuclear force.

(2) T h e n u c le a r f o r c e s e e m s I o b e in d e p e n d e n t o f e le c t r ic c h a rg e . T h is
means th at the nuclear interactions betw een tw o protons, tw o neutrons, or one
proton and one neutron are basically the same. F o r exam ple, from the analysis
o f proton-proton and neutron-proton scattering, scientists have concluded th at
the nuclear p art is essentially the same in both cases. Also th e facts that (a ) light
nuclei arc com posed o f equal numbers o f protons and neutrons, (b ) the binding
energy per nucleon is app roxim ately constant, and (c ) the mass difference o f
m irror nuclei (E xam p le 7.2) can be accounted for by the difference in coulomb
energy alone, indicate th a t the nuclear interaction is charge independent. B e­
cause o f this p rop erty, protons and neutrons are considered equ ivalen t insofar
as the nuclear force is concerned. F or that reason, as indicated before, th ey are
designated by the com mon name o f nucleons.

(3 ) T h e nuclea r f o r c e depen ds on the relative orien ta tion o f the spins o f

th e in tera ctin g nu cleon s. T h is fact has been confirm ed b y scattering experi­
ments and by analysis o f the nuclear energy levels. I t has been found that the
energy o f a two-nucleon system in which the tw o nucleons have their spins parallel
is different from the energy o f such a system in which one has spin up and the other
down. In fact, the neutron-proton system has a bound state, the deuteron, in which
the tw o nucleons have their spins parallel (S = I ), but no such bound state seems
to exist if the spins are antiparallel (.S' = 0).

(4 ) T h e nuclea r f o r c e is not c o m p le te ly centred; it depen d s on th e o rie n ­

tation o f th e spins relative to th e line jo in in g the tw o n u cleon s. Scien­
tists have concluded this b y noting th at even in the sim plest nucleus (th e deuteron),
the orbital angular m om entum o f the tw o nucleons rela tive to their center o f mass
is not constant, con trary to the situation when forces are central. T h erefore, to
explain the properties o f the ground state o f the deuteron, such as the m agnetic
dipole and electric quadrupole m om ents, w e m ust use a linear com bination o f s
(o r I — 0) and d (o r 1 = 2 ) w a ve functions. P a r t of the nuclear force seems to be
due to a rela tiv ely strong spin-orbit interaction. A n oth er part, called the tensor
force, closely resembles the interaction between tw o dipoles.

(5) T h e nuclea r f o r c e has a rep u lsive core. T h is means that at v e ry short

distances, much sm aller than the range, the nuclear force becomes repulsive. T h is
assumption has been introduced to explain the constant average separation of
nucleons, resulting in a nuclear volu m e p roportion al to the total number o f nu­
cleons, as w ell as to account fo r certain features o f nueleon-nueleon scattering.

In spite o f all this inform ation about nuclear forces, the correct expression for
the potential energy fo r the nuclear interaction between tw o nucleons is not y e t
well known. Several expressions have been proposed. One is the Y u la w a potential,
300 Nuclear structure C7.6

Ep Ep Ep

F ig. 7-7. Empirical shapes for the nuclear potential energy.

proposed about 193S by th e Japanese physicist H id e k i Y u k aw a, and given by

ο - τ >τ o
E p( r ) = — E 0r 0 — ^r - »

w here E 0 and r 0 are tw o em pirical constants. T h e constant r 0 is the range o f the

nuclear force and E 0 gives the strength o f the interaction. T h e decreasing expo­
nential factor e ~ rlr° drops the Y u k a w a poten tial energy to zero faster than the
electric poten tial energy, which varies as I /r. H o w ever, there are even some
doubts that the nuclear interaction can be described in term s o f a poten tial energy
function in the same w a y that we have been able to explain the g ravita tion al and
electrom agnetic interactions.
In any case, for m ost problem s the nuclear interaction at low energies m ay be
represented schem atically by a potential energy as shown in Fig. 7 -7 (a ). B eyond
a certain distance the poten tial energy is practically constant, or (which is equ iva­
len t) the force is zero. A t v e ry short distances a repulsive core m igh t be added
(F ig . 7 - 7 (b )). T h is is the ty p e of potential to be included in Schrodinger’ s equation
w hen w e discuss n-n and n-p interactions. F o r p-p interactions, however, w e must
also include the coulomb repulsion e2/ -ln t0r, which is im portant on ly outside the
range o f the nuclear forces (F ig . 7 - 7 (c )). T h e solution o f S clu odinger’s equation
then g ives the station ary states o f two-nucleon systems. Sometimes, to obtain
sem iqu an titative inform ation, one can replace the nuclear potential b y a square
poten tial well.
AVe cannot discuss nuclear structure w ith the same thoroughness as w e dis­
cussed atom s and molecules, since w e do not know the exact form o f the nuclear
poten tial energy to be incorporated in the Schrodinger equation. N evertheless,
the know ledge w e do have about nuclear forces is sufficient to p rovid e a sound
basis for discussing nuclear structure.
7.7) The ground slate of the deuteron 301

7.7 T h e G ro u n d State o f the O eu teron

T h e deuteron, com posed o f a proton and a neutron, is the sim plest o f all nuclei
(if we exclude the triv ia l case o f the nucleus o f hydrogen which is a single p roton ).
B asically, on ly the nuclear interaction is op erative in binding a neutron and a
proton togeth er (w e m ay neglect the small m agnetic interaction resulting from
their m agnetic m om ents). T h erefore, from a detailed analysis o f the properties
o f the deuteron, w e can obtain valu able inform ation about the nature o f nuclear
forces. T h e deuteron has on ly one stationary state (w hich ob viou sly is its ground
state) w ith an energy E = -E f1= — 2.224 M e V . Also the spin o f the deuteron is
I = I. W e m ay then assume th at the proton and neutron have th eir spins parallel
(th at is, S = I ) and th at the orb ital angular m om entum o f their rela tive m otion
around the center o f mass is zero (th a t is, L = 0 ), resulting in a state sS ]. In a
state 3S i there is no orbital m agnetic m om ent, and the m agnetic m om ent o f the
deuteron should be equal to μρ + μ„ = 2.7927 — 1.9131 = 0.8796 nuclear m ag­
netons, which is v e r y close to the experim ental valu e μ(ι = 0.8574 nuclear m ag­
netons. T h erefo re our assumption about the ground state seems to be well founded.
Considering th at the nuclear forces are central, w e m ay express the w a v e function
o f the deuteron in the same form as was done for an electron in E q. (3.18). In an
s-state the angular p art is constant (see T a b le 3 -5 ) and w e h ave to consider on ly
the radial p art R ( r ) = u (r )/ r , w here u (r) is obtained from E q. (3.24). S etting
I = 0 in th at equation, which corresponds to a 3S i state, and recalling th at m is
the reduced mass o f the neutron-proton system (th a t is, m ~ %mp), w e have

h*_ (E u
+ E p(r )u = Eu. (7.14)
2m dr2

L e t us next, for sim p licity, express the nuclear poten tial energy b y the square
w ell represented in F ig. 7 -8 (a ), which has a depth E 0 and a radius a * T h e problem

(a)

* The inclusion of a repulsive core would not substantially change the results we shall
obtain in this section, and for that reason we omit its consideration.
302 .Xuclear structure (7.7

then becomes identical to th at discussed in E xam p le 2.0, since the Schrodinger

equation for u (r ), E q . (7.14), is the same as for ^(.e) in that exam ple. W e conclude
that the form o f u (r ) is

. . ( A sin k,r, r < a,

U (r) = I f t - ', r > a,
where
kf = 2 m (E 0 - E b)/ h 2
and
a2 = 2 m E 0/h2.

T h is w a v e function is shown in Fig. 7 -8 (b ). T h e con tinuity o f the proper function

at r = a requires th at Eq. (2.23) hold, nam ely

k~i cot k,a = —a (7.15)

or
[2 m ( E u - E b)/ h 2\ '12 cot [2 m (E 0 - E b)/ h 2] U2a = - [ 2 m E 0/h2] ' 12.

In our case w e know E b and we m ay use this equation to obtain inform ation about
E 0 and a. Since there is on ly one station ary state, w e recall from E xam ple 2.6
that n 2h 2/8m < E 0a 2 < Dtt2Ii 2/8m. T h e ground state o f the deuteron deter­
mines on ly the valu e o f E 0a 2, w hich is about 1.48 X IO-28 McVr m 2. T o obtain
E 0 and a separately, we must h ave another relation. F rom scattering experi­
m ents we can estim ate the range a (see Section 7.8). Thus if a is o f the order o f
2 X IO-15 m, w e have th at E 0 is abou t 37 M e V . I t m ust be noted that if we
use som e oth er ty p e o f short-range poten tial instead o f a square w ell, w e obtain
differen t values o f E 0 and a.
W e indicated at the beginning th at there is a sm all discrepancy between the
values of Mu and μ 0 -f- Mn which must be accounted for. A lso the deuteron has an
electric quadrupole m om ent Q0 = 2.82 X IO-31 m 2 C. B ut a 3S j state is spheric­
a lly sym m etric and does not have an electric quadrupole m om ent. T h u s w e m ay
suspect th at our assumption o f a 3S j ground state for the deutcron is n ot com ­
p letely correct.
N o w a 3S 1 state is not the on ly state com patible w ith 1 = 1 . W e m ay also
h a ve the states 1P 1 ( L = I 1S = 0), 3P i ( L = I,S = I ), and 3D 1 ( L = 2, S = I).
I f the values o f mu and Qll are com puted for such states, th e results arc all v e r y d if­
ferent from the experim ental values. T o solve this dilem m a, w e m ay assume th at
the w a v e function o f the ground state o f the deuteron is a linear com bination o f
the four possible w a v e functions w e have m entioned. But the 3S i and 3D ] states
have even p a rity and the 1P 1 and 3P i states h a ve odd p arity. T h erefore, if the
ground state o f the deuteron has a well-defined p arity (as is to be expected if the
force is sym m etric in the tw o interacting particles), w e m ust com bine on ly the
3S i and 3D 1 states. Λ d etailed calculation, w h ich w ill be om itted, shows that to
reproduce the experim ental values o f mu and Qll w e must h a ve

* d ,u „.r o n = ( U ) S 1K 3S 1) + 0 . 2 0 v K :!D , ) .
7.8) Neulron-prolon scattering at low energies 303

T h e fact th a t w e h a ve to m ix .states w ith L = 0 and L = 2 shows th at the orb ital

angular m om entum o f the deuteron does n o t have a w ell-defin ed valu e and that
therefore the nuclear force is n o t rigorously central. In the deuteron, the non-
central part is attribu ted to th e tensor force.

7M X r u t r o n -I tVoton S ru llv rin g at Loir E n r r g iv s

A n oth er valu ab le source o f inform ation about the nuclear force betw een tw o nu­
cleons is scattering experim ents. T o p erform proton-proton scattering experi­
m ents, a beam o f protons from an accelerator is m ade to im pin ge on a target
containing hydrogen atoms, and the scattered protons arc analyzed. T h e d evia­
tion from pure coulom b scattering gives inform ation about the nuclear force.
Sim ilarly, in ncutron-proton scattering, a beam o f neutrons from a nuclear reactor
or oth er neutron source is p rojected on to a hydrogen target and the scattered
neutrons are observed. N eu tron-neu tron scattering experim ents are m ore d iffi­
cult, since it is impossible to have a target com posed on ly o f neutrons; therefore
some indirect m ethods are necessary.
L e t us now consider n-p scattering. Suppose th at a beam o f neutrons o f m om en­
tum p = hk m oves along the Z-axis, as in F ig. (7 -9 ). Thus the incident particles
m a y be described b y the w a v e function ^ mc = c 'k:. T h e current density cor­
responding to these particles I a j mc = «#in«|2 = v. W h en the neutrons pass close
to the target they are subject to the nuclear forces resulting from th eir interaction
w ith the protons and are d evia ted from their initial direction o f m otion. T h e scat­
tered neutrons at a great distance from the ta rg et are represented b y a w a v e func­
tion resem bling spherical w aves; th at is, th eir w a ve function Iuis th e form e'kr/r
(see P rob lem 3.30). T h e inten sity o f the scattering is not necessarily the same in
all directions, and in general depends on the angle 0 which the direction o f scat-

Scattcred neutrons

F ig. 7-9. Scattering of particles.

304 Nuclear structure {7.8

tering makes w ith the Z-axis. Thus w e m ay w rite ^ scat = }{ ff)c 'k'/ r, where J(O) is
called the scattering amplitude. T h e total w a ve function is

(7.16)

T h e flux o f particles scattered through the surface dS per unit tim e (F ig. 7 -9 ) is

i# sc»t| 2 = H /(0)12 d S /r2.

B u t d S/r2 is equal to the solid angle dQ subtended b y dS. Thus

F lu x o f particles scattered per unit tim e through dS = v\f(0)\2 dU.

T h e differential cross section σ (β ) is defined as

flux o f particles scattered per unit tim e within dil

σ

(7.17)

I f we observe σ {θ ) experim entally, w e m ay obtain J(O) b y ap p lyin g E q. (7.17).

T h en w e m ay look for the nuclear forces which g iv e the observed function /((?).
T h is provides a means o f guessing the nature o f the nuclear interaction.
W h en the energy o f the incom ing neutrons is v e ry low, w e m ay obtain a sim ple
expression for f (6 ). W e note first th at the incom ing beam is composed o f particles
o f m om entum hk, parallel to the Z-axis but m ovin g at differen t distances from the
axis and thus having differen t angular m om enta w ith respect to the scattcrer.
T h a t is, th e w a ve function e'kz does n ot g iv e inform ation about the position o f the
particles and w e m a y speak on ly o f the p rob a b ility th at a g iven incom ing p article
w ill h ave a certain angular m om entum . T h u s w e m ay say th a t the w a v e function
e'kz describes a beam o f particles having the same energy and m om entum but d if­
feren t values o f angular m om entum . In other words, w e m ay express e'kl as a
sum mation o f angular m om entum w a v e functions according to

Σ Ί'1' (7.18)

w here each ψι (called a partial w a v e ) corresponds to a g ive n angular m om entum

and has the sam e angular dependence as the functions Y io o f T a b le 3-5. (W e
m ust have mj = 0 because, if the particles m ove p arallel to the Z-axis, their
angular m om entum rela tive to the origin o f coordinates m ust be perpendicular to
th e Z-axis; th at is L z = 0.)
U sing a classical picture, w e m a y define the im pact parameter b as the perpendic­
ular distance from the Z-axis when the particle is still v e ry far to the left, so that
L = bp = bhk. B u t L = ftV T ( T F T ) ~ hk T h e refo re bk ~ I. Thus, according to
their angular m om entum , the particles fall w ith in the differen t zones shown in
Fig. 7-10. W h en the nuclear force is o f short range, there is appreciable scattering
7.8) Neutron-proton scattering at Ioio energies 305

F ig. 7-10. Angular momentum zones.

on ly if b is o f the order o f the range, or smaller. T h a t is, the on ly particles which

w ill be scattered out o f the incom ing beam are those having I < k X range. For
v e ry low energies, k is v e ry small and on ly particles w ith I = 0 are scattered. W e
say then th at w e have s-scattering. In quantal language w e m ay say that in the
presence o f a scatterer o f short range on ly th e I = 0 part o f the w a v e function
^ inc in E q. (7.18) (o r the partial w ave ^ u) o f a beam o f v e ry low -energy neutrons
is m odified, becom ing ψ'η, w h ile for I > 0 the ψι are the same as in E q. (7.18).
Thus the w a v e function m odified b y the scattering must be expressed as

i = Ψ'ο + Σ Φι·

I t can be shown th at the partial w a ve ip0 o f zero angular m om entum , corresponding

to the free-particle w a v e function ψ„
Kinc = eikz, is

sin kr
kr

T h e function λτψ 0 = sin kr is represented b y the dashed line in Fig. 7—11(b).

Er

Q ύ J f r

(a)
F ig. 7-11. (a) Rectangular deuteron potential well, (b) Positive energy wave functions.
306 Xurlear slructure (,7.8

T o obtain the m odified zero angular m om entum w a ve function ψ'0, we note th at in

the case o f a rectangular poten tial w ell, shown in F ig .·7 -1 1 (a), the p article is free
when r > a, but its w a v e function for r < a depends on the nuclear poten tial
energy. T h u s the w a v e function for r > a is still a frcc-particle solution, but
shifted along the radial direction so th at it joins sm ooth ly w ith the solution for
r < a (recall E xam p le 2.(5). W e must therefore w rite

,, sin( A r - M 0)
φ° = C Fr------

T h e qu a n tity δ0 is the phase shift. T h e w a v e function tr\p'0 = C sin (Ar -f- 50) is
represented by the solid line in Fig. 7 - 1 1(b). N o t e th at the am plitude o f ψ0 is
also differen t from that o f ψ0· T h e n it can be shown (see E xam ple 7.4) th at the
differential scattering cross section is given by

(7.19)

Since σ (θ ) is independent o f the angle 0, the scattering is spherically sym m etric.

T h e to ta l scattering cross section is

(7.20)

because the to ta l solid angle around the target is 4 π. F rom the observed valu e of
σ, we m ay obtain the phase shift A0 experim entally. On the other hand, if one
uses E q. (7.15), it can be shown th at a t v e ry low energies

hk?/‘2 m

H ence E q . (7.20) m a y be transform ed into

In scattering experim ents th e neutron and proton m ay h a ve their spins parallel

(trip let state) or antiparallel (single state) and th erefore we m ay determ ine whether
the force is or is not spin-dependent b y exam ining the cross section in each case.
E xperim ental results show th at the tw o cross sections are different, thus confirm ­
ing the spin-dependence o f the force. T h e depth and range for the trip let state,
when w e assume a square potential, have been found to be I i 0 = 26.2 M eV ,
a = 2.25 X IO- 15 m, w h ile for the singlet state w e m ust use I i 0 = 17.8 M e V
and η = 2.51 X IO-15 m.
A s the energy o f the incom ing neutrons increases, the scattering affects partial
w aves o f angular m om entum higher than zero. T h e effect on each partial w ave
ψι is described b y a corresponding phase sh ift 5/, so that the to ta l cross section is
given by

(7.22)
7.8) Neutron-proton scalterinij at low eneri/ies 307

O bviou sly E q . (7.20) corresponds to the case in which the on ly nonzero phase
shift is S0. T h e phase shifts Si are functions o f the energy. B y m easuring σ at
different energies and an alyzin g the angular distribution o f th e scattered p arti­
cles, we m ay obtain the Si’s experim entally. On the other hand, w e can com pute
the Si's th eoretically by assuming a reasonable poten tial energy fo r the interaction
between the incom ing particle and the scatterer. T h e refo re scattering experim ents
are v e ry useful in our search for the form o f the nuclear interaction.

E X A M P L E 7.1. Calculation of the cross section for s-scattering.

Solution: Combining Eqs. (7.16) and (7.18), \vc may write

I Arr

* =
I

which, when compared with Eq. (7.19), gives

ikr
Va = \h + m — ·
T

From the result of Problem 3.18 we know that = -I (sin kr)/r. A more detailed analysis
(which we omit) based on the normalization of the wave function indicates that we must
make A = I /k. Thus

, sin kr
= ^ T '

Also, as indicated previously in the text,

„ sin (kr + Sn)

Vo = C Fr--------

Hence we have that

c sin (kr + 5p) _ sin kr e^_

kr kr r

Recalling that sin a = (e'a — e ~ ‘a)/2i, after a simple algebraic manipulation we obtain
the scattering amplitude as

e’>0 sin Sn
m =
k*

Using Eq. (7.17), we may then write the differential cross section as

sin“ So
VO) = Im \ ~

which is the expression given in Eq. (7.19) for / = 0 or s-scattering.

308 !Vuclear structure (.7.8

db
----Z

F ig. 7-12. Coulomb scattering of a charged particle.

E X A M P L E 7.5. Calculation of the cross section for coulomb scattering of a charged

particle by a nucleus.

S o lu tio n : When a charged particle, let us say an electron, a proton, or an a-particle

(or He nucleus), passes near a nucleus it experiences an electric force which is repulsive
or attractive depending on the charge of the incoming particle. As a result, the incom­
ing particle is scattered or deviated from its original path. Let O be the position of the
nucleus and A the initial position of the projectile, very far from O (Fig. 7-12). The ini­
tial velocity of the particle, at A 1 is vo. The impact parameter b is the perpendicular dis­
tance from .4 to a line OZ passing through 0 and parallel to ro. Thus when the particle
is at .4, its ^ngular momentum relative to 0 is L - mvob. I f the force is central, the angu­
lar momentum remains constant during the process.
Given that re is the charge of the particle (r = — I for electrons, - r I for protons and
deutcrons, and + 2 for He nuclei) and Ze is the charge of the nucleus, the repulsive force
on the particle is

Under the action of this force the incoming particle describes a hyperbolic path, suffering
a deviation (or scattering) given by the angle Θ, which is a function of vo and 6, or (which
is the same) of the energy and angular momentum of the projectile.
When the particle is at any position, such as .1/, its angular momentum is mr2(d<t)/dl),
because r(d<f>/dt) is the component of the velocity perpendicular to r. Therefore, since
the angular momentum must remain constant because the force is central,

(7.24)

The equation of motion in the !'-direction is

7.8) Neulron-prolon scattering at low energies 309

Eliminating r - by using Eq. (7.24), we may write

2
dvu vZe . (ίφ
dt Airtonwob dt

To find the deflection of the particle, we must integrate this equation from one extreme
of the path to the other. A t .4 the value of v„ is zero because the initial motion is parallel
to the if-axis, and also 0 = 0. A t B we have vu = t’o sin 0 and φ = x — Θ. N ote that
at B the velocity is again t’o because, by symmetry (or the conservation of energy), the
velocity lost when the particle approaches O must be regained when it recedes from 0.
Then
/T0Sinff
/ T 0 S in ff λ
g rr—9
I J vZe I ■ u IJ
/ atv = r I sin φ άφ
Jo 4T€omvoo Jo
or
v7c"
vo sin Θ = - (I + cos Θ).
ATTtonwob

Remembering that cot. = ( I -j- cos 0)/sin 0, we finally get

j » . W i i. „ 2 5)

This relation gives the scattering angle in terms of the impact parameter b or the angular
momentum I. = mvob.
N ext we compute the cross section which was defined for the general ease by Eq. (7.17).
Suppose that a beam of particles coming from an accelerating machine is projected against
a target nucleus 0. The particles do not all have the same angular momentum or impact
parameter and therefore they will not all suffer the same deviation. Those deviated be­
tween the angles Θ and 0 -(- dO are particles having an impact parameter between b and
b -)-d b · that is, the particles falling on the shaded ring shown in Fig. 7-12, which
has an area 2ir6 db. Given that Ar is the number of particles per unit cross-sectional area
in the incident beam, then the number of particles passing, per unit time, through the
ring is i'o:V(2x6 db). This is the same as the flux of scattered particles per unit time
within the solid angle dV., defined by 0 and 0 + dO. The incident current density is ob­
viously f'o.V. Therefore, when we apply Eq. (7.17), the scattering cross section is

/m VoN(2Tb db) db
ac(0 ) = ------- =2x6 — . ( / .2 6 )
! ' O - Y dil

where the subscript C stands for coulomb scattering. From Eq. (7.25), we have

6 = (vZe2/Airtomvo) cot \θ

and therefore

db = — $(vZe~/Απίοηιΐ'ό) esc2 dO.

Also
dil = 2x sin Θ dO = 4x sin hO cos \0 dO.
310 Nuclear xlruclure , (7.9

Substituting these values in Eq. (7.26) and using only absolute values, since the negative
sign means only that Θ decreases when b increases, we get

2 „2 I

<rc(0) = V \ . esc4 id. (7.27)

4(4ττίο)·»ι Co

This result shows that particles scattered by an inverse-square law of force are distributed
statistically according to a esc4 &Θ law. Equation (7.27) was obtained by the British
physicist Ernest Rutherford (1871-1937) and was used by him and his collaborators, in
experiments performed during 1911-1913, to analyze the scattering of α-partides when the
particles passed through thin foils. The experimental verification of the esc4 iO law pro­
vided the evidence for the nuclear model of the atom, which has been accepted since then
as the correct atomic model.
I f the only force exerted by the target nucleus on the projectile is the coulomb repul­
sion, Eq. (7.27) would hold at all energies. But when the projectile has an angular mo­
mentum (or impact parameter) small enough and an energy high enough so that the
projectile passes very close to the nucleus, deviations from a c ( 0 ) may arise if a short-
range nuclear force exists in addition to the coulomb force. From the analysis of these
deviations, we may compute the phase shifts for the nuclear effects. These computations
provide information, for example, about the nuclear force between two protons.
When the projectiles are energetic electrons, they may penetrate through the nucleus.
This also introduces a deviation from a c ( 0 ) , which in this case is due to the charge dis­
tribution within the nucleus. From the analysis of these deviations, the curves shown in
Fig. 7-2 were obtained by R. Hofstadter and his collaborators.
Note that, in the above discussion, we have used a classical description of the coulomb
scattering which may seem an uncalled-for departure from the procedure for describing
nuclear scattering in the preceding section. However, mathematical calculations of cou­
lomb scattering using quantal methods are rather involved and beyond the scope of this
book. One reason for this difficulty is that the coulomb force, given by Eq. (7.23), is of
long range and therefore affects all partial waves in Eq. (7.18), even if the energy is very
low. On the other hand, coulomb scattering is one of the cases in which the classical
and quantal descriptions agree in their results. It can be shown that the scattering
amplitude for coulomb scattering is given by

MO) = esc2 " ■ « - * » + » '» (-.28)

2(47r«o)»u’o

which, when substituted in Eq. (7.17), gives the same value of ac as Eq. (7.27). In the
above equation, 7 = vZes/4wtofivo and tjo is a constant which depends on 7.

7.it Tlu- SIh -II Motlt-I

A basic goal o f nuclear physics is to determ ine the m otion o f the nucleons in a
nucleus, and from the m otion to d e riv e nuclear properties, both in the ground and
the excited states. T h e problem is m ore com plex than in the atom ic case, due to
the lack o f a dom inant central force and the existence o f tw o classes o f particles—
neutrons and p roton s--ea ch class separately ob eyin g the exclusion principle.
7.9) The shell model 311

16O at 6.8 MeV

F ig. 7-13. Energy of the first excited state for even-even nuclei.

H ow ever, there is strong eviden ce indicating th at each nucleon m oves in an aver­

age field o f force which is produced by the other nucleons and which, in a first
approxim ation, m ay be considered central. Thus, using an independent-particle
model as w e did for the electrons in an atom, w e should characterize the nucleon
energy states by quantum num bers n and I, g ivin g the energy level and th e orbital
angular m om entum . Quantum number n is chosen to label the order o f increasing
energy in which successive levels w ith the same I appear. Thus Is, 2s, 3s, . . . , etc.
mean the first, second, third, and so on, levels, all w ith I = 0, in order o f increasing
energy.
In the same w a y that atom s exhibit a shell structure, and have com plete shells
when all occupied energy levels have th eir full qu ota o f electrons, nuclear levels
also exhibit a shell-like structure. Since there are tw o classes o f particles in a nu­
cleus, there is a double-shell arrangem ent, one for protons and another for neutrons.
A t certain values o f Z or .V corresponding to com plete shells, nuclei result which are
particularly stable, in the same w ay that in ert gases consist o f atom s w ith certain
com plete electronic shells. T hese values o f Z or N (com m on ly called “ m agic
numbers”) are 2, 8, 20, 28, 50, 82 and 120. F or example, Fig. 7-13 shows the
energy o f the first excited state o f several even-even nuclei. M agic-n um ber nuclei
show an abnorm ally high first excitation energy, suggesting th a t at the m agic
numbers there is a large energy gap between the last filled energy level or shell and
the next em p ty state. T h is is also the case for the atom s o f inert gases (recall
Fig. 4 -5 ). S im ilarly, the number o f stable isotopes and isotones w ith Z or Ar equal
to a magic-number, respectively, is rela tiv ely large (F ig. 7-14). A lso the neutron
312 Nuclearstruclure (7.9

Number o f neutrons, .Y

F ig. 7-14. Number of stable nuclides as a function of (a) the atomic number, (b) the
neutron number.

capture cross section o f nuclei w ith m agic-num ber N is extrem ely low (F ig . 7-15),
indicating a v e ry weak binding o f the extra nucleon.
T o explain the values o f the m agic numbers, M . G. M a y e r and J. H . D . Jensen
proposed independently in 1949 that, in addition to the average central force,
there is a strong spin-orbit interaction in nuclei (n o t necessarily o f electrom agnetic
origin, as in the case o f the atom ic electrons discussed in Section 3.9) which acts
on each nucleon and which is proportional to L - S . T h e existence o f a spin-orbit
interaction is am ply supported b y experim ental evidence (see n ote at end o f this
section). Since S can be either parallel or antiparallel to L , g ivin g differen t values
o f the to ta l angular m om entum J = L + S, each (n, I) level is separated into tw o
7.9) Theshellmodel 313

Number o f neutrons
F ig. 7-15. Cross section for neutron capture as a function of the number of neutrons.
[Adapted from B. Flowers, P ro g .in N u c. Physics 2, 235 (1952); London: Pergamon Press]

levels by the spin-orbit interaction, w ith the low er energy corresponding to L and
S parallel. Thus a nucleon energy state is characterized b y the quantum numbers
n, I, j , where j = I ± F o r a given I, the state havin g j = I r j has low er
energy than the state w ith j = I — £. T h is is con trary to the electronic case in
atoms, and shows th at the nuclear spin-orbit interaction cannot be o f electro­
m agnetic origin. Since

L S = i(J 2 - L 2 - S 2)

= i { j ( j + i ) - K i + D - m 2

= I i lh 2, j = i + h
\ -W + w 2, j =

the separation between tw o states w ith the same I but different j is proportional
to 21 -]- I, and therefore increases w ith I. T h e degeneracy o f each n, I, j state is
2) + I, corresponding to the 2; + I possible orientations o f J rela tive to a given
axis. Thus, according to the exclusion principle, the m axim um number o f neutrons
or protons in a given n, I, j level or shell is 2 j + I ; that is,

5 7 9 11 13
j i I 2 "T ΊΓ

Max. n u m b e r of
2 4 6 8 10 12 14 ...
p ro to n s o r n e u tro n s
31't Nuclear structure (7.9

nl

Ip- Ip-

Protons Neutrons

F ig. 7-16. Proton and neutron energy levels in the shell model. [Adapted from P. F. A.
Klinkenberg, Rees. Mod. Phys. 2-t, 03 (1952)]

A s for the atom ic electrons, each nucleon state is designated by the letters s, p, d,
etc., corresponding to the valu e o f I, and a subscript g ivin g the valu e o f j . Thus
for I = O w e h ave an s 1/2 state, for I = I w e have states p i/2 and p 3/2, for I = 2
the states arc d 3/2 and d 5/2, and so on.
T h e arrangem ent o f single-particle energy levels for protons and neutrons is
shown schem atically in Fig. 7-16, which indicates how each (n , I) level, due to the
average central force, is split b y the spin-orbit interaction. T h e p a rity o f each
level is g iven by ( — 1)*· T h e ordering o f levels follow s the requirem ents o f the
experim ental evidence. T h e energy gaps at the m agic numbers are clearly shown.
T h e y occur e v ery tim e a new high value o f I appears, producing a large spin-orbit
7.9) The shell model 315

splitting. T h e slight difference between proton and neutron levels is due to the
coulomb repulsion between the protons. Several em pirical central force potentials
have been proposed to reproduce the experim ental ordering o f the levels, but none
has yet a full theoretical and experim ental basis.
I t has been observed th a t all even-even nuclei have zero spin in their ground
state, w h ile in odd- A nuclei, havin g Z even and Ar odd (o r the reverse), the nuclear
spin I coincides w ith the ,/-value o f the last odd nucleon state in m ost cases (in a
few cases it is ecpial to j — I ) . I f the odd nucleon o f an o d d -.4 nucleus is excited
to a nearby state, the nuclear spin o f the excited state gen erally coincides w ith the
new j-v a lu e o f the excited nucleon. Hence, when an (n , l , j ) level is being filled, it
seems that identical nucleons pair their total angular m om enta so th at if the
number o f identical nucleons in the (n, I, j ) state (proton s or neutrons) is even,
their resultant angular m om entum is zero, and if it is odd, their resultant angular
mom entum is j (o r j — I ). F or odd-odd nuclei (o f w hich there are on ly four
stable ones), it is m ore difficult to determ ine the nuclear spin, and all integral
values o f I from j v + j n to Jjp — /n| are allow ed in principle, w here j p corresponds
to the unpaired proton and Jn to the unpaired neutron. In certain cases the largest
possible valu e o f I is preferred and in others the smallest.
A n independent-particle shell m odel cannot account for these coupling or pairing
rules o f the angular m om enta o f the nucleons. T h ese rules are attributed to
the so-called “residual” interaction, i.e., the difference between the actual nuclear
interaction experienced by a nucleon and the average central plus spin-orbit force
introduced in the shell m odel. T h e residual interaction contributes to the nuclear
stability by w h at is called a pairing-energy effect. W e can see this stabilizin g effect
from T a b le 7-2, which shows the number o f d ifferen t ty p es o f stable and alm ost
stable (or lon g-lived ) nuclides. T h e re is an obvious m a jo rity o f stable even-even
nuclides.

T A B L E 7-2 N u m b e r o f S tab le an d Very

L o n g -L iv e d N uclides

Z U Stable Long-lived

Even Even 155 11

Even Odd 53 3
Odd Even 50 3
Odd Odd 4 5

T h e shell m odel has been rather successful in predicting m any properties o f

nuclear states. In som e instances rather elaborate calculations are required. H o w ­
ever, in m any cases the shell-m odel calculations fail to explain the experim ental
facts accurately. F o r exam ple, electric quadrupole m om ents calculated using the
shell m odel are consistently too small, especially in the regions between m agic
numbers or closed shells.
Because o f the strong coupling am ong the nucleons, there arc several collective
effects in a nucleus. N ucleons occupying the core, composed o f com plete shells,
 ft

316 Nuclear structure (7.9

behave in a w ay rather similar to a liquid drop, which is capable of sustaining

oscillations in shape around an equilibrium spherical shape. T h e collective oscil­
lations occur w ith constant volume, and each nucleus m ay have several normal
modes of oscillation. Nucleons occupying the outermost unfilled shells exert a
sort of polarizing action and tend to give the nucleus an equilibrium nonspherical
shape closely resembling a prolate or oblate ellipsoid. This deformation is particu­
larly large in the regions 90 < N < 114 and 88; this acc
tiv e ly large electric quadrupole moment of such nuclei, which cannot be explained
by the shell model.
A theory has been developed which combines the shell model and the collective
effects. I t is called the unified model of the nucleus, but its analysis is beyond the
level of this text.

Note: Experimental evidence of the spin-orbit interaction in nuclei

We have presented the nuclear spin-orbit interaction as a convenient assumption to ex­
plain certain features of nuclear energy levels. However, is there direct experimental
evidence of such spin-orbit interaction? The answer is yes, and it comes from the analy­
sis of scattering experiments. In the same sense that the interaction between a magnetic
field and a dipole magnetic moment (which is of the form —(B · M ) implies a torque
which tends to align M parallel to (B, a spin-orbit interaction of the form —f ( r ) L · S
implies a torque that tends to align S parallel to L (with the opposite result if we have a
positive sign).

• Spin up
o Spin down
Unpolarized
proton beam

Fig. 7-17. Double scattering experiment.

Suppose that an unpolarized beam of protons (i.e., with their spins oriented at random)
is thrown against helium nuclei, as shown in Fig. 7-17. Consider those protons which
are scattered in the plane of the figure, and use the helium nucleus which is the scatterer
as reference to measure the orbital angular momentum. The protons scattered along
path (I) have their orbital angular momentum L “up” and those along path (2) have L
“down.” The spin-orbit interaction of the protons with the helium nucleus favors protons
with their spins parallel to L along each path, and therefore protons along paths (I) and
(2) preferentially have their spins up and down, respectively, and the two beams are
each partially polarized. Next, beam (I ) suffers a second scattering by another helium
nucleus which splits it into beams (3) and (4) with L up and down, respectively. Protons

M
7.9) The shell model 317

along path (3) have their spins preferentially up and those along path (4) have their
spins preferentially down. Since more protons in beam (I ) have their spins up than down,
the spin-orbit interaction favors scattering into beam (3) over beam (4). Therefore detec­
tor D I should register a larger proton current than . This is what is observed in the
experiment. In the absence of a spin-orbit interaction, beams (3) and (4) should have the
same strength. Therefore experimental evidence clearly supports the existence of a nuclear
spin-orbit interaction, as manifested by the polarization produced by scattering.

E X A M P L E 7.6 . Calculation of the magnetic dipole moment of an odd-A nucleus using

the shell model.

Solution: In an odd-A nucleus having Z odd and N even (or the reverse), the magnetic
moment, according to the extreme independent-particle shell model, is attributed to the
odd nucleon. AU the other nucleons have their resultant angular momenta paired in
opposite directions and therefore do not contribute to the resultant nuclear magnetic
dipole moment. Let us consider a nucleon having an orbital angular momentum L and
spin S. According to Eq. (7.3) and (7.5), we may write the angular momentum of a
nucleon in a form valid both for neutrons and protons as

M = (e / 2mp)(g iL + gsS), (7.29)

where gi = -\-l for protons and zero for neutrons and the values of gs were given in Sec­
tion 7.4 for both kinds of nucleons. Since both L and S are precessing around their re­
sultant J, the average or expectation value of M has the direction of J and is given by

M a v e = M · U j U j = —
M
J,J T

where u j is a unit vector in the direction of J. The component of M ave along the Z -
axis is
M 2,ave = (M · J/J2) J 2 = (M · J/J2)mh
= (eh/ 2 mp) { ( giL + gsS) · ///2R (7.30)

As explained in Section 7.4, the tabulated value of the magnetic moment μ is by definition
the value of M 2iave when m has its maximum value (in our case, when m = j ) divided by
Mn = eh/2mp.Thus, recalling that J 2 = j ( j + l)ft2, we have

(A7z,&ve)m=j *iL
g J “f”* J
(7.31)
M = m { j + i w

But
L tJ = i ( J 2 L 2 — S2) = ■§■[ / 0 “h i ) / - 1(1 H- I)
- f -

S - J = U J 2 - L 2 + S2) = U j U + I) - w + D +

Introducing these results in Eq. (7.31), we have that for the two cases of ± £ the
magnetic moment is
3IS Nuclear structure (7.9

j =/

F ig. 7-18. Magnetic dipole moments and Schmidt lines for nuclei with odd Z.

J=I

F ig. 7-19. Magnetic dipole moments and Schmidt lines for nuclei with odd N .

In the independent-particlc shell model we have that, for odd A , the nuclear spin is
considered equal to the angular momentum of the unpaired particle. Therefore, setting
I = j in Eqs. (7.32) and introducing the values of <ji and g, for protons and neutrons, we
obtain two sets of values for μ, depending on whether Z or N is odd, as a function of the
nuclear spin. These arc called Sclimidl lines; they are represented in Figs. 7-18 and 7-19
for odd Z and odd ,V, respectively. The actual experimental values are indicated by
crosses for j — I -J- £ and by circles for j = I — J. W e can see that most of the
7.10) Xuclear radiative Iransilions 319

magnetic moments do not lie on either of the Schmidt lines but in the region between
them. The lack of precise agreement is not surprising, since the independent-particle
shell model is a rather crude one. I f one uses the unified model of the nucleus, it is possible
to obtain a better agreement.

7.10 \ U f I f 1I i r H a d iu tirv Tra nsition s

In addition to the ground-state configuration, a nucleus m ay h ave several excited
states. These m ay be classified into tw o groups: particle excitations and collective
excitations. In a particle excitation, one or m ore nucleons are shifted to another
level o f higher energy w ith ou t essentially m od ifyin g the m otion o f the other nu­
cleons. P article excitation energies are o f the order o f one M eV .
A s explained in the previous section, nuclei which are in regions far from m agic
numbers and w hich have incom pletely filled shells are n ot spherical, but resemble
prolate or oblate ellipsoids. In these deform ed nuclei, as in molecules, the principal
axes rotate in space, resulting in a collective rotation in which all nucleons partiei-'
pate. T h e rotational energy is quantized, and therefore a deform ed nucleus has
several rotational energy levels. F o r even-even nuclei, the rotational energy levels
arc given by

A’ rot = ^ / (/ + I ), (7.33)

where I is the angular m om entum o f rotation o f the w h ole nucleus, which, for
sym m etry reasons, can take on ly even values; that is, / = 0, 2, 4, . . . T h erefore
all rotational levels have even p arity. T h e effective m om ent o f inertia o f the nu­
cleus is 3, and it is alw ays less than the mo­
ment o f inertia which w e obtain when we K, keV
consider the nucleus as a rigid ellipsoid, be­ - 10S5 E. kcV
cause not all nucleons participate in the — 514
same w ay in the rotational m otion. I ig-
ure 7-20 shows the rotational energy levels
for lsoI I f and 238Pu. These energy
levels clearly follow the pattern given by
Eq. (7.33). F o r nuclei other than even-even
ones, the arrangem ent o f rotational levels -041.7
-303.7
is m ore com plex.

-309.3 -I4G.0

2 · -----------93.3------------------------2+ ----------44.11

F ig. 7-20. R o ta tio n a le n c rg y le v e ls o f180H f --------() 0 '-------0

and 238Pu. ‘ *«0| If 23sPu
320 Nuclear structure {7.10

In addition, there m a y be several vib ration a l excited states associated w ith the
collective oscillations m entioned in the preceding section. These excited v ib ra ­
tional states are separated b y the same energy Ιιω, w here ω is the vib ration a l
angular frequency. F o r even-even nuclei the resultant spin or angular m om entum
o f the first exaited vib ration a l state has a valu e o f 2, and the second excited v ib ra ­
tional state m ay h a ve a spin o f 0, 2, or 4. B oth levels have even p arity. F igu re 7-21
shows som e vib ration a l levels o f 82K r, 126T e , 130X e and 102P t. B oth collective
rotation a l and vib ration a l excitation energies are in general m uch less than par­
ticle excitation energies, and am ount to a few keV . T h is accounts for the low-
ly in g first excited levels o f highly deform ed nuclei w hich lie between m agic-num ber
nuclei, as shown in F ig. 7-13.

0*. 2*, 4+, 6 r

0\2+,4+

Kn

2+ 2’ 2+ 2+ 2*

C+
Theoretical w Kr l2eT c l3eX e l02Pt
scheme

F ig. 7-21. Vibrational energy levels of some nuclei.

N u clei w hich h ave com plete shells are spherical, and do not exhibit low -lyin g
rotation a l or vib ration al levels. N u clei w ith alm ost-com plete shells are on ly
sligh tly deform ed, and do not exhibit rotational excited levels but on ly v ib ra ­
tional levels. F ro m our discussion w e see th at the energy levels o f a nucleus are
as com plex as those o f a molecule. H o w ever, to th eoretically p redict the energy
levels o f a nucleus is m ore difficult than to predict those o f a m olecule because of
our incom plete know ledge o f the nuclear interaction.
A nucleus m a y be carried to an excited energy level when it absorbs a photon
o f the proper energy or when it undergoes an inelastic collision w ith a nearby pass­
ing fast particle, such as a proton or a neutron. I f the p article is charged, this
latter process is called coulomb excita tion ; it is v e r y useful for studying the low-
ly in g energy levels o f deform ed nuclei.
A n excited nucleus m ay g iv e off its excess energy and undergo a transition to
the ground level w ith emission o f electrom agnetic radiation, called, for historical
reasons, gamma rays. Thus the nuclear gam m a-ray spectrum is sim ilar in origin
to atom ic and m olecular spectra. T h e 7-spectrum results from the readjustm ent
7:10) Nuclear radiative transitions 321

keV kcV
% Ϋ. -419 (JorJ)+ - -722
-390
hV“ ‘
(J or J ) ' - -037
d§+- -340

dV- -247

<r -304

ι.γ - -163

Sj+ -80
— 0 d j+ -0
(Cd

F ig. 7-22. Radiative 7-transitions of "g C d , 1I 1Xe, and 'I 11Xe.

of the m otion o f the nucleons in a transition between tw o nuclear stationary

states. Som e 7-transitions o f 1H C d 1 1I j X e 1 and 1I j X e are shown in Fig. 7-22.
T h e angular m om entum and p a rity of each level is given on the le ft and the energy
of each le v el relative· to the ground state appears on the right.
Although, in atoms and molecules, on ly electric dip ole transitions are im portant,
higher electric and m agnetic m ultipole transitions are often im portant in nuclei,
especially in collective transitions in which m any nucleons participate. E lectric
and m agnetic transitions are designated b y the sym b ol E or M follow ed b y the
numeral I, 2, 3 , . . . g ivin g the valu e o f AJT and corresponding to dipole, quadrupole,
octupole, etc., radiation. T h e ty p e o f transition is determ ined b y the change ir.
angular m om entum and in p a rity o f th e nucleus, according to the follow in g scheme:

Spin
2
►
<1

I 3 4
II
»4

change

Ycs El M2 E3 M4
Paritv
change No Ml E2 E4
M3

R a d ia tiv e transition probabilities depend on the energy difference between the

tw o states in vo lved , the mass number o f the nucleus, and the spin change. The
transition p ro b ab ility increases as the energy change increases and decreases as
the valu e o f A l increases. T h erefore, for a given energy change, the larger th e d if­
ference in angular m om entum between an excited state and the ground state, the
lower the transition p rob ab ility and the longer the lifetim e o f the excited state,
unless there is the possibility o f a transition to another excited state o f low er
322 Nuclear structure C7.10

F ig. 7-23. Lifetimes for single-particle transitions involving a proton for a nucleus with
mass number approximately 100, as predicted by the shell model.

energy w ith a sm aller change in angular m om entum . F igu re 7-23 shows the life­
tim es o f excited states, as a function o f the energy absorbed or em itted, for d if­
feren t m ultipole transitions in vo lvin g a proton, calculated using the shell model,
fo r a nucleus w ith mass number about 100.
C o lle c tive rotational and vib ration a l transitions, w hich h ave A l = 2 (and no
change o f p a rity ), are o f ty p e E2, or electric quadrupole transitions. Observed
electric quadrupole transitions in m any nuclei w ith unfilled shells have transition
probabilities th at are larger than the values predicted b y the shell model. T h is
suggests a rather large electric quadrupole m om ent for these nuclei as com pared
w ith shell-m odel calculations, and hence a rela tiv ely large deform ation (recall
F ig. 7 -4 ). I t was this fact which g a v e the in itial impetus to the collective m odel
o f the nucleus.
F ro m F ig. 7-16, w e can see that in o d d -d nuclei h a vin g Z o r N sligh tly less than
th e m agic numbers 50, 82, or 126, there are nearby en ergy levels w hich differ
g re a tly in angular m om entum . T h is gives rise to excited states havin g rela tiv ely
lon g lifetim es. F o r example, in 137B a ( Z = 56 and N = 81), which has one neu­
tron less than the m agic number 82, the odd neutron m a y be either in the 2d 3/2,
3si/2 or I h 11/2 states. A c tu a lly the ground state corresponds to the configuration
in which the odd neutron is in state 2d3/2 and the next excited state corresponds
to a configuration in which the odd neutron is in state I h 1!/2 (F ig . 7 - 2 4 (a )). T h e
difference in energy o f the tw o states is 0.661 M e V . A transition betw een the tw o
7:10) Nuclear radiative transitions 323

210 I I I I I ' I I I I I I I I

220
I '·
2.6 mill
M eV - 1
V" -0.661 200 .1

-
··
ISO •
M4
•
160 - -

140
- -
r-
137Ba 120 jp/
:
(a) " I • -
I
100
Ii
—

Ir M eV 80 _ 'KJ _

114 mill
r - -0.041
60

E3 40

20
I+- -0.009
Ml . I I I I i . . . . I I I

r- -0 O 10 60 SO 1 too 120 140

83K r 20 50 82 126
(I.) Odd nucleons. ·Ν or · Ζ — ♦

F ig. 7-24. Isom erictransitionsin Fig. 7-25. Long-lived isomers of odd A . [Adapted
137Ba and 83Kr. from M . Goldhaber and R. D. Hill, Revs. Mod.
Phys. 24, 179(1952))

states corresponds to A l = 4 and a change in p arity, and thus is an M 4 transition.

T h e observed lifetim e o f the excited state is about 2.C min. A n oth er exam ple is
83K r (Z = 36 and N — 47). T h is nucleus has three neutrons less than m agic
number 50. T h e states com peting for the ground-state configuration are 2 p i;2
and I go/2- T h e first state has spin k and odd p arity. T h e second configuration
could have spin J or § w ith even p arity, g ivin g rise to the energy levels shown in
Fig. 7 -2 4 (b ). T h e observed transition is / = 4 ~ —> / = f + and is an E3 transi­
tion w ith an energy o f 0.032 M e V . T h e lifetim e o f the / = i state is about 114 min.
N u clei w hich are in excited states and which have a reasonably long lifetim e are
called isom ers. Transitions for which A l > 3 are designated as is o m e ric tra n s ition s .
F igure 7-25 shows the distribution o f nuclei having isomeric states. T h e y appear
in groups called isla nds o f is om erism , which fall just below the m agic numbers,
according to the predictions o f the shell model. In fact, the explanation o f
these islands o f isom erism is one o f the successes o f the shell model.
324 Nuclear structure

U e ferfin e v tt

1. “The Nuclear Force,” R. Marshak, Sci. Am ., March 1960, page 98

2. “ Nuclear Models,” It. van Wageningen, Am. J. Phys. 28, 425 (1960)
3. “ Pauli and Nuclear Spin,” S. Goudsmit, Physics Today, June 1961, page 18
4. “ The Nucleus T od ay,” D. Bromley, The Physics Teacher 2, 260 and 320 (1964)
5. “ Problem of Nuclear Structure,” V. Weisskopf, Physics Today, July 1961, page 18
6. Nuclear Forces, D. Brink. N ew Y ork: Pergamon Press, 1965
7. Structure of Atomic Nuclei, C. Cook. N ew Y ork: Van Nostrand, Momentum-Books,
1964
8. Structure of Matter, W. Finkelnburg. New Y ork: Academic Press, 1964, Chapter 5,
Sections 1-8
9. Foundations of Modern Physical Science, G. Holton and D. H. D. Roller. Reading,
Mass.: Addison-Wesley, 1958, Chapters 36, 37, 38
10. Principles of Modern Physics, R. Leighton. New Y ork: McGraw-Hill, 1959, Chap-
p ters 13, 14, 16, 18 and 19
11. Nuclear Physics, I. Kaplan. Reading, Mass : Addison-Wesley, 1963
12. Introduction to the Atomic Nucleus, J. Cuninghamc. Amsterdam: Elsevier Publishing
Co., 1964

Problfitns

7.1 Examine Fig. 7-1 (or the chart of
nuclides provided with the text) carefully
to verify the statement that adjacent stable
isobaric pairs do not occur in nature.
7.2 M ake a list of all adjacent stable iso­
topic sets larger than 4. For example,
titanium (Z = 22) has five adjacent stable
isotopes. Use Fig. 7-1 or the chart of nu­
clides provided with the text.
7.3 With the aid of Fig. 7-1 (or the chart
of nuclides), investigate stable isotonic
sets. W rite the neutron number N for sets
of more than four stable isotones. Are any
of these adjacent stable isotones?
7.4 Ordinary boron is a mixture of the
10B and 11B isotopes. The composite (or
chemical) atomic mass is 10.811 amu.
W hat percentage of each isotope is present
in natural boron (a) by number and (b) by
mass?
7.5 Calculate the nuclear radius of 10O,
120Sn, and 208Pb.
7.6 Choosing the most abundant isotope,
compute the nuclear radius for nuclides
with Z equal to 10, 30, 50, 70, and 90.
Also compute the radius of the inner elec­
tronic orbit, using Eq. (3.11). Plot both
radii on the same graph. Draw conclusions
about the interaction of inner electrons
with the nucleus.
7.7 What nuclei have a radius equal to
one-half the radius of 236U?
7.8 Estimate the kinetic energy of a nu­
cleon inside a nucleus, both by using the
quantum-mechanical picture of a particle
in a potential box of width IO-15 m and
by considering the de Broglie wavelength X
of the nucleon, which is of the order of 2-irr,
where r is IO-15 m.

7.9 The interaction between the electron
and the nuclear magnetic moments gives
rise to a hyperfine splitting of the atomic
energy levels. The energy due to this inter­
action is proportional to
( μ ο / 4 ι τ ) μ χ μ Β ( ί ·~ 3)a ve,
where r is the distance of the electron from
the nucleus. Show that the hyperfine split­
ting is of the order of IO-5 eV in energy,
giving rise to a hyperfine structure of spec­
tral lines which is of the order of IO-2 A
when the lines are in the visible range.
7.10 The hyperfine splitting of atomic
energy levels discussed in the previous
problem is also proportional to I ■ J, where
I is the nuclear spin and ./ the electronic
angular momentum. Analyze the hyper­
fine splitting of the electronic states 2S 1/2,
2P 1/2, and 2P 3/2 of 23N a (/ = § ). In each
case determine the number of levels and
their relative spacing. Show your results
on an energy level diagram.
7.11 The electric quadrupole moment of
an ellipsoidal charge distribution which
has axial symmetry is Q = §Z (a - — 62),
where a is measured along the symmetry
axis and b is measured along the perpendic­
ular direction. The mean nuclear radius R
is defined by R - = ab2. (This guarantees
that a sphere of radius R has the same
volume as the ellipsoid.) Show that if
a = R-\~ A R , then b = R — $ A R and
Q = ^ Z R A R , to the first order of approxi­
mation. Also note that Q /ZR2, which is
plotted in Fig. 7-4, is proportional to
A R /R . Determine whether this plot is
more informative than a plot of the qua­
drupole moment alone, as far as information
about nuclear deformation goes.
7.12 Using the data of Table 7-1 and the
results of Problem 7.11, estimate A R /R
for 176Lu1 which is one of the most highly
deformed nuclei.
7.13 Estimate the coulomb repulsion
energy of the two protons in 3IIe (assume
that they are 1.7 X 10 ~ ’ 5 m apart).
Problems 325
Compare this energy with the difference
in the binding energies of 3H and 3He.
Is the result compatible with the assump­
tion that nuclear forces are charge inde­
pendent?
7.14 How much energy is required to re­
move (a) a proton and (b) a neutron from
16O and from 17O? Is the result an indica­
tion of the existence of pairing forces?
7.15 From the atomic masses given in
Table 7-1, calculate the total binding
energy and the binding energy per nucleon
for 'L i, 16O, o7Fe, and 176Lu.
7.16 The empirical Weiszacker formula,
Eq. (7.11), contains four terms. Plot each
of the terms as a function of .1. For the
appropriate Z and N values for the fourth
term, use those corresponding to the most
stable isobar and choose only selected A
values. Determine the relative importance
of each term in the different regions of the
periodic table.
7.17 With the aid of Eq. (7.13), determine
the atomic number of the stable nuclide for
.1 = 27, 64, 82, 125, and 180. Compare
these values with the data in Fig. 7-1.
7.18 Using the Weiszacker formula, cal­
culate the atomic masses of 12C, 27Al, 88Sr,
185Re, and 232U. Compare with the values
listed in Table 7-1 and judge the accuracy
of the formula.
7.19 Using the Weiszacker formula, cal­
culate the mass difference between the
mirror nuclei 23N a and 23M g. Compare
with the result using the experimental
values of the masses, which are 22.98977
and 22.99412 amu, respectively.
7.20 (a) Calculate the binding energies
for 14O, 13O, lfiO, 17O1 18O, and 19O.
(b) Repeat for 11C 1 13N 1 16O, 17F, and
18Ne. (c) From the results of (a) and (b),
cxirlain the variation in binding energy
as a neutron or a proton is added to a
nucleus. The masses of those nuclei not
listed in Table 7-1 are (in amu): 14C,
14.00324; 14O 1 14.00860; 13O, 15.00307;
18O, 17.99916; 190 , 19.00358; 17F 117.00209;
18Ne, 18.00571.
326 Nuclear structure
7.21 The following mass differences have
been found experimentally:
1I I 2 — 2H = 1.5434
3 2II — i 12C = 4.2300
12C 1I I 4 - 16O = 3.6364
10 " 27.26
On the basis of 12O = 12.000 amu, calcu­ scattered when it approaches a gold nu­
late the atomic masses of 1I I 1 2H, and lfiO.
Compare with the experimental values.
7.22 A simple empirical approximation for
the nuclear potential is the Yukawa poten­
tial Jip = — /ioroe-r/ro r , where
Eo = 50 M eV and ro = 1.5 X 10~l a m.
Plot the Yukawa potential for r = O.lro,
O.oro, ro, 1.5ro, 2ro, and 3ro, and compare
with the electric potential energy of two
protons at the same separations.
7.23 Show how the 3S, 1P 1 3P 1 and 3D
states of a neutron-proton system are the
only ones compatible with a nuclear spin
equal to one.
7.24 It can be shown that, when all phase
shifts are considered, the scattering ampli­
tude /(0) of neutron scattering is given by
](θ ) ν'4 π (2 / + D t V
k I
where Θ is the scattering angle and the l ‘io
are angular momentum functions. When
the energies are not too great, only the
first two phase shifts, ίο and Si, are needed
to describe the neutron scattering and all
other phase shifts arc zero, (a) Write /(0)
and the differential cross section α(θ) for
this approximation, (b) Show that the
scattering is not spherically symmetric.
How do you correlate the asymmetry with
the signs of the phase shifts? (c) Compute
the total cross section by integration and
verify that it coincides with the first two
terms in Eq. (7.22). [H in t: Use the expres­
sions for Poo and P io given in Table 3 I.]
7.25 Show that, in an elastic scattering
experiment involving protons on protons
or neutrons on protons, no particles are
scattered more than 90° in the laboratory
frame of reference. (Assume equal masses.)
[H int: Use the nonrelativistic formulas
X 1 0 -3 amu,
relating the scattering angle in the C- and
X lO ^Λ-frames
’ amu, of reference given in the appendix.)
X
amu. Through what angle in the laboratory
frame of reference is a 4-M cV a-particle
cleus with an impact parameter which is
2.6 X I O - 13 m?
7.27 What is the impact parameter of a
4-M eV α -particle, given that. it. is scattered
through an angle of 15° by a gold nucleus?
7.28 Find the distance of closest ap­
proach for (a) IO-MeV and (b) 80-MeV
protons, incident head-on on a gold nu­
cleus, and compare with the nuclear radius,
(c) In which ease will the proton “ hit” the
nucleus? Find the kinetic energy of the
proton when it “hits” the nucleus.
7.29 An aluminum foil scatters IO3 a-
parlieles per second in a given direction.
I f the aluminum foil is replaced by a gold
foil of identical thickness, how many a-
particles will be scattered per second in the
same direction?
7.30 The number of α-particles scattered
i i Sin Sl Y l0l by a given foil is IO6 per second at a scat­
tering angle of 10°. Calculate the number
of α-particlcs scattered at each 10° interval
up to 180°. Plot your results for σ(0).
7.31 A beam of 12.75-MeV α-particlcs is
scattered by an aluminum foil. It is found
that the number of particles scattered in a
given direction begins to deviate from the
predicted coulomb scattering value at ap­
proximately 54°. I f the α-particles are
assumed to have a radius of 2 X 10_ , ° m,
estimate the radius of the aluminum nu­
cleus. [H in t: It can be shown that the dis­
tance of closest approach is given by
r — ( vZe2 4xeo»H 'o)(l-|-esc 20)·]
7.32 A t what neutron energy docs the
relation k X range of nuclear force = 0.5
hold? Could this result be used to estimate
the upper limit of the energy at which only

s-scattering of neutrons by protons need be
considered ?
7.33 Calculate the nuclcon-nucleon scat­
tering cross section in the limit of low
energies, E - * 0, for the triplet potential
IEo = 36.2 M eV ) and the singlet poten­
tial (E 0 = 17.8 M cV ). What cross section
would be measured experimentally if the
spins of the particles were to be oriented
randomly?
7.34 Calculate the cross section for nu-
cleon-nucleon scattering in the triplet
state (E o = 36.2 M eV ) for E = 0.1, 0.5, I,
and 5 M eV. Do you conclude then that at
low energies the cross section for nucleon-
nucleon scattering is not sensitive to the
energy?
7.35 (a) Using the shell-model scheme
given in Fig. 7-16, find the nucleon con­
figuration for 2H 1 3H 1 3He, 4H e1 7Li, 12C,
13C, and 30Cl. (b) Predict the nuclear spin
for these nuclides. Compare with the values
listed in Table 7-1.
7.36 Compute the magnet dipole moments
of the nuclei listed in the previous problem,
using the method of Example 7.6, and
compare with the experimental values
given in Table 7-1.
7.37 The moment of inertia of a nucleus
of mass M and average radius R, if con­
Problems 327
sidered a solid sphere, is β = f . l / Λ 2.
W ith a mass number .4 equal to 50, 100,
and 150, estimate the energy (in M eV ) of
a Ύ-ray emitted in a transition from a
rotational energy level with I - 2 to one
with I = 0. Compare with the energy of
Ύ-rays emitted by even-even nuclei in those
regions. What do you conclude?
7.38 From the rotational energy levels
shown in Fig. 7-20, estimate the moment
of inertia of 180Hf. The moment of inertia
about the symmetry axis of an ellipsoid of
revolution is S = §.l/62, where 6 is the
length of the other semiaxes. Estimate the
deformation A R / R of l80Hf, and compare
with the value obtained from the electric
quadrupole moment. [H int: Recall from
Problem 7.11 that 6 = R — % A R .[
7.39 Referring to Fig. 7-22, determine the
energy and multipole order of the 7-transi­
tions shown for each of the three nuclei.
7.40 Refer to Fig. 7-22(a) and (b ), and
assume that each of the levels shown is due
to a single particle transition; with the aid
of the shell-model level scheme of Fig. 7-16,
write the configuration for the ground state
and each of the excited states.
7.41 Referring to Fig. 7—22(c), deter­
mine whether or not the level scheme can
be attributed to rotational collective
excitations.
NUCLEAR PROCESSES

8.1 In lrod ud ion

8.2 Radioadive Decay
8.3 A lpha Decay
8A Bela Decay
8.5 Nuclear Reaclions
8.6 Nuclear Fission
8.7 Nuclear Fusion
8.8 Tlie O rigin of Ihe Elemenls
8.2) Radioactive decay 329

II. I In troiIin sIion

In the previous chapter w e an alyzed the basic properties o f nuclei, considered as

stable assemblies o f nucleons, and proposed a m odel which, in a m ore or less sat­
isfactory w ay, accounts fo r such properties. A n oth er source o f inform ation about
nuclear structure is the analysis o f processes, such as nuclear disintegrations and
nuclear reactions, in which there is a rearrangem ent in the energy or configuration
o f the nucleons. In this chapter w e shall analyze som e nuclear processes. M a n y o f
them occur naturally, but others are produced artificially in the lab oratory using
different typ es o f accelerating machines or nuclear reactors. T h e experim ental and
theoretical discussion o f nuclear processes is still an unfinished chapter o f con­
tem porary physics, in which a large am ount o f research is being done.

it.'2 Ila ilion rtin · H o r n y

W e rem ind the student that, when we were discussing Fig. 7-1, w e indicated that
some nuclei have a com bination o f protons and neutrons which does not lead to a
stable configuration. T h ese nuclei are therefore unstable or radioactive. U nstable
nuclei tend to approach a stable configuration by releasing certain particles. These
particles, when th ey were first observed a t the end o f the last century by J. B ec-
querel, Pierre and M a rie Curie, and others, were designated as a - and /3-particles.
A lp h a particles are helium nuclei, com posed o f tw o protons and tw o neutrons
as m a y be verified by m easuring their charge and mass. T h u s when a nucleus
emits an alpha p article its atom ic number Z decreases by tw o units and its mass
number A decreases by four units. T h e new nucleus therefore corresponds to a
different chemical elem ent. F o r exam ple, when the rad ioactive nucleus 2g?U em its
an α-parlicle, the residual nucleus is 2ISTh.
B eta particles are electrons which carry a charge — e. Hence, when a nucleus
emits a /3-particle, the atom ic number o f the nucleus increases b y one unit, but the
mass number does not change. F or exam ple, when the rad ioactive nucleus 2SjjTh
emits a /3-particle, the residual nucleus is 2StPa. Som e nuclei, instead o f em ittin g
electrons, release positrons which carry a charge -fe ; therefore the residual nucleus,
after positron emission, has an atom ic number sm aller by one unit. F o r example,
when the nucleus 12N em its a positron, the residual nucleus is 1|C. T h e tw o types
o f /3-decay are designated β ~ and β + , respectively. T h e residual or daughter
nucleus is som etim es left in an excited state and in the transition to its ground
state em its gam m a rays, as explained in Section 7.10.
M a n y isotopes o f elem ents w ith Z > SI (o r A > 20G) are n aturally radioactive.
A few other naturally existing lighter nuclei, such as u C and 40Iv, are also radio­
active. M a n y m ore rad ioactive nuclei have been produced in the lab oratory using
nuclear reactors and particle accelerators. F igu re 8-1 shows one o f the three natural
rad ioactive chains, the so-called u ra nium series, and T a b le 8-1 g ives the relevan t
inform ation about this series. T h e mass number o f nuclei in this series is given b y
4 « -f- 2, where n is an integer. T h e tw o other natural rad ioactive chains are the
actinium series and the thorium series, com posed resp ectively o f nuclei o f ty p e
 (£.2
330 Nuclear processes

Atom ic number

F ig. 8-1. The naturally radioactive uranium or 4n + 2 series.

4 n + 3 and 4n. T h e heavier nuclides in these tw o series are 2^ U and 2goTh. It

is suggested th at the student m ake a p lot o f these tw o series, sim ilar to Fig. 8-1,
using the chart o f nuclides p rovided w ith the text.
In the next tw o sections we shall
present a m ore detailed analysis o f a - and
/3-decay. B u t let us now discuss certain
features th at are com mon to both radio­
active processes. I t has been observed
that all rad ioactive processes follow an
exponential law. T h erefore, if N 0 is the
initial number o f unstable nuclei, the
number o f nuclei rem aining after a tim e
I is given by
N = N 0e ~ u , (8.1)

where λ is a constant characteristic of

each nuclide, called the disintegration
constant. I t is expressed in s-1 (o r in the
reciprocal o f an y other tim e un it). E qu a­
tion (8.1) is represented in Fig. 8-2. For
F ig. 8 2. Radioactive decay as a function
each radioactive nuclide there is a fixed of time.
8.2) Hadioaclive decay 331

TABLE 8—1 The Uranium Scries

T yp e of Particle
Disintegration
Radioactive species Nuclide disinte­ Half-life energy,
constant, s-1
gration M eV

Uranium I (U I) 238T
92UT a 4.51 X IO9 y 4.88 X i o - 18 4.19
231-1.1
Uranium X i (U X i ) 90 I n β 24.1 d 3.33 X ΙΟ "7 0.19
Uranium X 2 (U X 2) 234Pa
91* “ β 1.18 m 9.77 X IO-3 2.31
Uranium Z (U Z ) iItPa β 6.66 h 2.88 X 10~5 0.5
Uranium I I ( U l I ) 2IiU a 2.48 X IO5 y 8.80 X IO -14 4.768
Thorium (T h ) 2IoTh a 8.0 X IO4 y 2.75 X I O - '3 4.68
Radium (R a) 225Ra a 1620 y 1.36 X IO - 11 4.777
Radon (R n) 2IlR n a 3.82 d 2.10 X IO "6 5.486
Radium A (R a A ) 2ItPo Of, β 3.05 m 3.78 X 10~3 a: 5.998
0 :?
Radium 11 (R ah) 2I 4
2Pb β 26.8 m 4.31 X 10-4 0.7
Astatine-218 (2l8A t) 2I 8A t a 1.3s 0.4 6.70
Radium C (R aC ) 2IlOi a, β 19.7 m 5.86 X 10-4 a : 5.51
/3:3.17
Radium C ' (R a C ') 2IJPo a 1.64 X IO -4 s 4.23 X IO3 7.683
Radium C " (R a C ") 2ItT I β 1.32 m 8.75 X IO -4 1.96
Radium D (R a D ) 2ISPb β 21 y 1.13 X 10-9 0.0185
Radium E (R a E ) 210IU
S3**1 β 5.0 d 1.60 X 10-° 1.155
Radium F '(R a F ) 210Pn
si1 0 a 138.4 d 5.80 X 10“ 8 5.300
200-TM 4.2 m 2,75 X 10-3 1.51
Thallium-206 ( 206T l) SI 1 1 β
Radium G (R aG ) 20eP
82* h
13 Stable

tim e in terval T , called the half-life, during which the number o f nuclei a t the be­
ginning o f the interval is reduced, by the end o f the interval, to one-half. So if
w e in itia lly had N 0 nuclei (or atom s), a fter tim e T on ly N 0/2 are left, a fte r tim e
2T on ly N 0/4 remain, and so on. T o find this tim e T, we set N = ^ N 0 and I = T
in E q . (8.1). Then $ N 0 - N 0e ~ XT or ex r = 2. T a k in g logarithm s, w e have
\T = In 2 = 0.693 or

T = 0.693/X, (8.2)

which relates T and λ. T h e recorded half-lives g o from a great m any years— such
as the h a lf-life o f the α-decay o f 209Bi, which is abou t 2 X IO 18 years, and the
β ~·-decay o f 115In , which is about 6 X IO u years— down to fractions o f a second
( 8B e has ;ui α -decay half-life o f the order o f IO- 10 s).
F rom E q. (8.1) we can find the rate a t which nuclei disintegrate:

d N /d t = — \ N 0e ~ u = -\ N . (8.3)
332 Nuclear processes (8.2

T h is indicates th a t the disintegration rate dN/dt is proportional to the number o f

nuclei present. T h erefo re the disintegration rate dN/dt decreases in the same
proportion and w ith the same half-life as the number o f nuclei N . T h e absolute
value o f the disintegration rate, \dN/dt\, is called the activity o f the substance.
D isintegration rates are usually expressed in curies, abbreviated C i, in honor o f
P ierre and M a rie Curie, discoverers o f polonium and radium. T h e curie is defined
as the a c tiv ity o f a substance in which 3.700 X IO 10 nuclei disintegrate per second.*
Subm ultiples o f the basic unit are the m illicurie ( I m C i = IO-3 C i) and the micro-
curie ( I p C i = 10-B C i).
E quations (8.1) and (8.3) are both statistical laws which are valid on ly when
the number o f nuclei is v e ry large, and which m ay be interpreted in the follow in g
way. T h e re is a decay probability per u n it time X th at an unstable nucleus w ill
disintegrate according to a specific process. T h e p ro b ab ility that the nucleus w ill
disintegrate in the tim e interval dl is X dt. I f there are N nuclei present (w h ere N
is v e ry large), then we m ay expect a number o f nuclei equal to (λ d t)N to disinte­
grate during dt. T h erefo re we m ay w rite

dN = — (X d t )N or dN/dt = — XN,

which is E q . (8.3). T h e minus sign appears because N decreases w ith tim e as a

result o f the decay. T h e calculation o f the decay p ro b ab ility per unit tim e X for
each decay process is an im portant problem for which refined techniques o f quan­
tum mechanics must be used. N o te from the ab ove discussion th at w e cannot
speak o f the half-life o f a single nucleus or predict w ith certainty when a given
nucleus will disintegrate, and we repeat th at Eqs. (8.1) and (8.3) are correct on ly
in a statistical sense.

E X A M P L E 8.1. Compute the mass of 1.00 Ci of 14C'. The half-life of 14C is 5570 years.

S o lu tio n : S in c e T = 5570 y r = (5.570 X IO3 yr) X (2.156X 107 s/yr) = 1.758X IOn s,
the disintegration constant is λ = 0.693/T = 3.94 X 10_ , 2 s_ I . Also

IA V M l = I Ci = 3.70 X IO7 s ~ l .

Therefore, using Eq. (8.3) with absolute values, we find that

N = = 9.38 X 10IS nuclei of 14C 1

which is also the number of carbon atoms present. The atomic mass of 14C is 14.0077 amu.
Thus the mass of the above number of carbon atoms is

.1/ = (14.0077 X 1.6604 X IO-27 kg a t o m - ') X (9.38 X IO18 atoms)

= 2.18 X IO -7 kg.

* This rate is approximately equal to the activity of I g of 11a.

8.2) Radioaclire decay 333

E X A M P L E 8.2. One method of producing a radioactive nuclide is to place a sample of

a given substance inside a nuclear reactor. Radioactive nuclides are produced as a result
of neutron capture by the nuclei of the substance. For example, when we bombard
59Co with neutrons, we find that we obtain 60Co, which is ^-radioactive with a half-life of
5.27 years. Another method of obtaining radioactive nuclides is to bombard the sub­
stance with charged particles, such as protons or deuterons, using accelerators to energize
the projectiles. In both cases the new nuclide is produced at the constant rate of g nuclei
per second. Calculate the number of nuclei of the radioactive nuclide produced in terms
of time.
X/-V1I1UX

F ig. 8-3. Production of a radioactive nuclide as a function of time.

S o lu tio n : The radioactive nuclide is fabricated at the rate of g nuclei per second, but
at the same time, according to Eq. (8.3), the nuclide disintegrates at the rate of λ .V
nuclei per second, where N is the number of nuclei present at that instant. Thus the net
rate of increase of nuclei per second* is

rf.v
Ti = 3“ λΛ ·

Separating the variables and integrating, we have

Γ , [ ‘ „ , .V - g/\
= - λ ί.
L 0T T ^ = - x L dt or 1o r T T = I T x

Assuming that the number of nuclei of the substance was initially zero (that is, N o = 0),
we have, at a later time t,

N = f ( I — β_λ<).
A

The maximum number of radioactive nuclei that can be produced under these conditions
is N max = ff/λ. The variation of N with I is illustrated in Fig. 8-3. N ote that at time
t = T 1 we have 0.50sA atoms and at I = 2 T we have 0.75g/λ atoms.

* The student should recognize that this equation is mathematically identical to that for
free fall of a body in a viscous fluid or for the growth of an electric current through an
inductance.
334 Nuclear processes (£.2

E X A M P L E 8.3. Substance A disintegrates into another substance B, which is also

radioactive. Given that Xa and Xs are the respective disintegration constants of A and B,
find the variation of B as a function of time. Assume that the initial amount of B is zero.

S o lu tio n : According to Eq. (8.3), substance A disintegrates at the rate

(IN λ /dt = —X aV a1

so that ,Va = ,Vaoe- V ''. For each nucleus of A that disintegrates, one of B is formed.
Thus B is formed at the rate of XaVa nuclei per second. A t the same time, however, it
disintegrates at the rate of Xs-Vs nuclei per second. Therefore the net increase of nuclei
of B per unit time is

~ = Xa-Va - X sV s or ^ = XaVaoe- "'1' - XsVs-

dt at

The solution of this equation which satisfies the condition that V s = 0 at time t = 0,
as the student may verify by direct substitution, is

N b = - xV Vao(e-X'1' - e- "* ').

Xs — Aa

I f substance B disintegrates into a stable substance C, then the number of nuclei of C

increases steadily until, after a very long time compared with the half-lives of A and B 1

F ig. 8—I. Radioactive series with three members. Only the parent, A (T a = I hr) is
initially present. The daughter, B, has a half-life of 5 hr and the third member, C, is stable.
8.3) Alpha decay 335

the number of nuclei of C is equal to JVao- The variation of Ν λ , N b , and N e with time
is illustrated in Fig. 8-4. A t the beginning we note that B increases because it is pro­
duced faster than it disintegrates. But, after a certain time, the situation reverses be­
cause the activity of the parent substance has decreased. The results can be extended to
more complicated radioactive chains .4 —> / } —> C —♦ Z) —> ■ ·· , such as the natural radio­
active series. A study of these chains is useful, for example, when we wish to determine the
age of rocks containing radioactive substances by finding the proportion of each sub­
stance in a sample of the rock.

S. 3 A lp h a U o v a y
A s we saw in the previous section, alpha decay consists in the emission o f an a -
particle (o r helium nucleus ^H e), composed o f tw o protons and tw o neutrons. T h e
daughter nucleus has an atom ic number tw o units less and a mass number four
units less than the parent. Thus, if we denote the parent and daughter nuclei by
X and Y , respectively, we m ay w rite the process o f α -decay as

iX - * I z t Y + tH e . (8.4)

F o r exam ple, 2g|U is an α -em itter and disintegrates according to the scheme

238tt 234rpi I 4 rjn

92 U —> 9o I h -p 2fie .

M ost α -em itters are h eavy nuclei, corresponding to nuclides at the end o f the p eri­
odic table. In fact, it can be shown from the expression for the nuclear binding
energy, as given by E q. (7.10), th at most nuclei w ith A > 1.50 should be a-em itters.
H ow ever, the m a jo rity o f α -em itter nuclei have A > 200. I t is supposed that,
with a few exceptions, the half-lives o f lighter nuclei for α -decay are so lon g th at
this decay m ode is p ractically unobservable.
A n «-p a rtic le is a dou bly m agic nucleus consisting o f tw o protons and tw o neu­
trons, all in an S i/2 shell, havin g a zero total spin and even parity. Thus a-particles
have an extraordinary stab ility, and therefore behave in m any instances as a single
unit or particle, sim ilar to protons and neutrons. T h e student m ay recall th at
R u th erford used α -particles as projectiles to probe the interior o f the atom and
establish the nuclear model.
W e m ust not think, how ever, th at α -particles exist as such inside the nucleus.
Supposedly there are certain correlations in the m otion o f the nucleons which
occasionally cause some o f them to group them selves into an «-p a rticle-lik e con­
figuration which, for a short tim e, acts as a dynam ical unit. W h en such a unit is
near the surface o f the nucleus, there is a certain p rob ab ility th at the group o f
nucleons escapes as an «-p a rtic le .
T h e poten tial energy o f interaction o f an alpha particle w ith the rest o f the nu­
cleus, which is v e ry sim ilar to th at o f a proton w ith the rest o f the nucleus (recall
F ig. 7 -1 ), is indicated in F ig. 8-5. T h e energy o f the α -particles (abou t 4 to 9 M e V )
is less than the height o f the coulomb barrier (abou t 40 M e V for m ost a-cm ittcrs)
at the surface o f the nucleus, and the «-p a rtic le can escape on ly by penetrating the
336 Nuclear processes (8.3

/Nuclear
I attraction

F ig . 8-5. Potential energy of an a-particle

and a nucleus.

F ig. 8-6. Tracks of α -particles in a cloud

chamber. The deviated track appears to be
due to the reaction 14N (a, p ) 170 which has taken place with a hydrogen atom in the
chamber. T w o groups of α-particles, each with a characteristic range, are clearly recog­
nizable in this photograph.

poten tial barrier (Section 2.8). W e can com pute the disintegration p ro b ab ility
per unit time, λ, in terms o f the p rob ab ility P o f p enetrating the barrier. T h e quan­
tity P is com puted using the m ethods o f quantum mechanics. T h e results agree
fa irly w ell w ith the experim ental values for λ.
F rom Fig. 8 -5 we see th at the higher the kinetic energy Eka o f the a-particle
the sm aller the height and w idth o f the barrier, and therefore the larger the prob­
a b ility P o f penetrating the barrier. Thus we m ay expect that the disintegration
constant λ w ill increase w ith Eka, a fact w e can v e rify b y inspecting T a b le 8-1.
A detailed calculation shows th at the transmission p rob ab ility P is v e ry sensitive
to the height and w idth o f the barrier, and thus to Eka- T h is explains w h y (as
seen in T a b le 8 -1 ) a change o f Eka b y a factor o f about tw o from 4.20 M e V
(w h ich corresponds to 238U ), to 7.G8 M e V (w hich corresponds to 214P o ), results
in a change o f λ from 4.88 X IO -18 s —1 to 4.23 X IO3 s_ 1 , or a factor o f about IO 21.
Since α -particles are charged, th ey ionize the atom s o f the substance through
which they propagate. T h is constitutes one o f the m ethods by which a-particles
can be detected, using devices which either measure the am ount o f ion ization (such
as ionization cham bers) or m ake the ionization visible (as in cloud cham bers).
F igu re 8 -6 shows a cloud-chamber photograph o f α -particle tracks m ade by a radio­
ac tiv e sample. A s a result o f the ionization, the α -particles lose energy u n til they
slow down sufficiently to pick up tw o electrons and becom e neutral helium atoms.
I t was R u th erford w ho (in 1919) first dem onstrated th at α -particles are helium
 Alpha decay 337

nuclei b y collecting (in an evacuated tube) the α-particles ejected from a substance;
when an electric discharge was passed through the tube, the spectrum o f helium
was observed.
T h e range o f α -particles depends on both their energy and the substance through
which th ey m ove. T h e ir range in air at S T P is on ly a few centim eters. F o r ex­
ample, α -particles from 210P o (5.3 MeAr) and from 214P o (7.7 M e V ) have ranges
in air o f about 3.8 cm and 7.0 cm, respectively. H ow ever, α -particles are easily
absorbed by a sheet o f paper o r a v e ry thin aluminum foil. In F ig. 8 -6 w e observe
that the α-particles producing the tracks fall into tw o groups, each with a charac­
teristic range.
T h e fact that the α -particles em itted by a given nuclide have a well-defined
range is an indication th at th ey also have a well-defined energy. Figure 8-7 shows
the energy spectrum o f the α-particles em itted by a number o f different nuclides.
T h e energy, in arbitrary units, corresponds to the channel numbers o f an energy-
analyzing device. One can clearly see th at the α -particles from each nuclide have
a well-defined energy. T h is fact confirms that α -decay is a tw o-b od y problem , as
expressed b y E q . (8 .4 ); thus α -dccay resembles the explosion o f a grenade into tw o
fragm ents. W e assume that, in the process o f α -dccay, energy and m om entum are
conserved. I f Q is the energy released in the decay o f the parent nucleus X , as­
sumed at rest in the laboratory, the kinetic energies o f the α -particle and the
daughter nucleus I ' a fter they are far apart [sec A p pendix I I , E q. (A . 27)] are

E ka = - — + m - Q, E kr = g * - - Q. (8.5)
m a -·- m y m a -f- m y

Clianncl number (energy)

Fig. 8-7. The α-particle energy spectrum from a sample of radio-thorium ( - 28T h ) and
its descendants. [From the National Nuclear Energy Series, Vol. 14A, The Actinide
Elements, G. Seaborg and J. Katz, editors. New York.: McGraw-Hill, 1954, Chapter 16.
W ith the permission of the United States Atomic Energy Commission.]
338 Nuclear processes C8.3

ICncrgy above ground

state o f T h C " , M cV

F ig. 8-8. Disintegration scheme for «-decay of 212Bi to 208Tl.

ICnergy above ground ICnergy above ground

state o f T IiD , M c V level o f T h C ', M eV

F ig . 8-9. Disintegration scheme for α-decay of 212Po to 208Pb.

8.3) Alpha decay 339

T h e value o f Q is obtained from the mass change in the process; that is,

Q = (wi.v — m y — m a) c 2, (8.6)

since η ίχ ο 2 is the internal energy o f the parent nucleus and m y c2 and mac 2 are the
internal energies o f the tw o products (see Ap p en d ix I I , E q. (A . 22)]. O f course, for
α-particle emission to occur, it is necessary that Q > 0. I f the masses are ex­
pressed in amu and Q is expressed in M c V , then E q. (8.6) becomes

Q = 931.48(mjr — m y — ma). (8.7)

In this equation the masses m ay correspond either to the nuclei or to the atoms,
since the electron masses cancel when atom ic masses are used.
S tric tly speaking, the α -particles from a given nuclide do not all have the same
energy; rather th ey exh ibit a certain fine structure. F o r example, the a-particles
from 238U have energies o f 4.18 M e V and 4.13 M e V . T h e reason for this is
that, although the parent nucleus m ay be in its ground state, the daughter nucleus
m ay be form ed in its ground state or in an excited stationary state. T h is situation
is illustrated in Fig. 8-8, which shows the decay scheme o f 212B i (o r T h C ); the
six «-p a rtic le transitions (as well as the subsequent 7-rays e m itted ) are indicated
by the arrows. In other cases, the reverse situation occurs. T h e parent nucleus
m ay be in the ground state or in one o f several excited slates, and the daughter
nucleus be in the ground state, as shown in F ig. 8 -9 for the disintegration scheme
o f 212P o (o r T h C '). Som e 7-transitions are also shown.

E X A M P L E 8.4. Compute the kinetic energy of α -particles emitted from 2jjlU.

S o lu tio n : The decay process is 2Ij2U —> 2IoTh + IjHe. The masses which are in­
volved are m x = To(232U ) = 232.1095 amu, my = m (228T h ) = 228.0998 amu, and
ma = 4.0039 amu. Applying Eq. (8.7), we obtain Q = 5.40 M eV. A positive Q means
that the process is exoergic and may occur spontaneously. B y use of Eq. (8.5), we compute
the kinetic energies as EkTh = 0.10 M eV and Eka = 5.30 M eV. W e obtain this value of
E ka assuming that the 2IoTh is in its ground state. But if 2<j8T h is left in an excited state,
then the value of E ka is less. The experimental value of the most energetic a-particles
from 232U is E k = 5.32 M eV, so that our theoretical interpretation seems to be correct.

E X A M P L E 8.5. Discuss the stability of 2Ij2U relative to the emission of other kinds of
particles.

S o lu tio n : W e may wonder if, in addition to α-decay, some nuclei exhibit proton, neu­
tron, deuteron, or some other type of decay. N o such decays have been observed because
the Q-values for these processes are negative. Therefore these decays cannot occur unless
energy is supplied and the parent nucleus is raised to an excited state, which may happen
in certain nuclear reactions. As an illustration, we may compute the Q-values for the
emission of several kinds of particles from the 232U nucleus, using Eq. (8.7) with ma and
my replaced by the corresponding masses of the emitted particle and the daughter nu­
cleus. The results are listed in Table 8-2. AU Q’s are negative, so that 232U is stable
against decay into such products. The reason α -emission by 232U is possible lies in the
relatively small mass of the «-particle due to its relatively large binding energy.
300 Nuclear processes {8.0

T A B L E 8-2 (i-V a lu c s fo r E m ission o f Different

N u c le a r P articles from 232U

Particle Mass Daughter Mass Q, M eV

n 1.0090 231U 231.1082 — 7.16

P ( 1H ) 1.0081 23lPa 231.1078 - 6.05
d (2H) 2.0147 230Pa 230.1060 — 10.4
t ( 3H ) 3.0170 229Pa 229.1033 -1 0 .1

it. t H e ia U e e a y
In Fig. 7-1 the stable nuclei were designated b y black squares. In such a figure,
those nuclei lyin g ab ove the stab ility region em it electrons (charge — e), a process
w e have called &~-decay. A n experim ental result is that the daughter nucleus,
although it has the same mass number, has an atom ic number larger b y one than
the parent nucleus. T h a t is, it appears th at in β ~·-decay a neutron is replaced by
a proton, and parent and daughter nuclei are isobars. T h e process can thus be
expressed by

ix -> z + i Y + e- (8.8)

N o te that the total charge is conserved, since the charge on the le ft o f E q. (8.8)
is Ze and on the righ t it is ( Z + l ) e — e — Ze. A lso the to ta l number o f nucleons
is conserved, since A remains the same. F o r exam ple, 14C is a β ~·-em itter and
transform s according to the scheme

1^C -> I47N + e -

S im ilarly , in Fig. 7-1, those nuclei ly in g below the stab ility region suffer β + -decay,
a process which consists in the emission o f positrons (charge + e ) . Positron s are
particles w ith the same mass and spin as electrons, but th eir charge is positive
instead o f negative. Positrons were predicted first on theoretical grounds by
P . A . M . D irac in 1927 (as a result o f some requirem ents o f the th eory o f rela­
tiv it y which w e cannot m ention here) and were observed for the first tim e in cosmic
rays by C. Anderson in 1932. I t has been verified that, in 0 + -decay, the atom ic
number o f the daughter nucleus is sm aller by one u n it (again in agreem ent w ith
the law o f conservation o f charge) but th at its mass number is the same as th at of
the parent nucleus (in agreem ent w ith the conservation o f nucleons). T h u s it
appears that in /3+ -decay a proton is replaced b y a neutron. T h erefo re the process
m ay be expressed by

ίΧ -> z _ l Y + e + . (8.9)

A s an exam ple, 11C is a /3+ -em itter and transform s according to the scheme
 (f)

F ig. 8-10. Disintegration schemes for various /3-emitters, (a) 20F 1 (b) 14O 1(c) 27M g 1
(d) 38CI1 (e) 140L a 1 and (f) 64Cu.

In some instances it has been observed th at the parent nucleus, instead o f em it­
ting a positron, captures an electron from one o f the innerm ost atom ic shells, let
us say a K -electron . These are s-electrons. A s the reader m ay recall from Sec­
tion 3.5, s-electrons have v e ry penetrating orbits which reach v e ry close to the
nucleus; therefore th eir p ro b ab ility o f being captured b y a proton is rela tively
large. T h is process, called electron capture (E C ), also results in the replacem ent o f
3U2 IVuclear processes {8Λ

a proton by a neutron in the daughter nucleus. I t can be expressed by

z X -f- e — —» Y- (8 .1 0 )

O nce m ore note th a t the electric charge and the nucleon number are conserved in
the process. E lectron capture is follow ed by x-ray emission by the daughter
nucleus when an outer electron falls into the vacan t state le ft in the K-shell. These
x-rays are the same as the characteristic rays o f the daughter atom , discussed in
Section 4.7.
A s in α-decay, the daughter nucleus resulting from /3-decay or E C m ay be left,
in its ground state or in an excited state; in the latter ease the process is follow ed
b y 7-emission. Figure 8-10 shows the disintegration schemes o f some beta em itters.
One o f the m ore interesting features o f /3-decay is that the electrons and positrons
are em itted w ith a wide range o f kinetic energies (and m om enta), from zero to a
m axim um com patible w ith the total energy available. In other words, the elec­
trons and positrons have a continuous energy spectrum. Figure 8-11 (a ) shows
the energy distribution o f the electrons resulting from the /3~-decay o f 2 n B i (o r
R a E ) and Fig. 8 - l l ( b ) shows the energy distribution o f the positrons em itted in
the /S+ -decay o f 13N. B u t Eqs. (8.8) and (8.9) are tw o-b od y processes, sim ilar to
α-decay, and the laws o f conservation o f energy and m om entum require th at in
the center-of-mass fram e o f reference, in which the parent nucleus is at rest, the
energy availab le (the Q o f the process) must be split in a fixed ratio am ong the
daughter nucleus and the electron or positron (recall E q. 8.5 for «-d e c a y ). T h is is
in contradiction to the experim ental result we have mentioned.
T o settle this new difficulty, P auli suggested in 1930 th at another particle must
also be in vo lved in /3-decay, so th at three particles result. T h e third particle has

Kinetie energy o f electrons, M cV Kinetic energy o f positrons, M eV

(a) lb)

F ig. 8-11. (a) The energy spectrum of the electron emitted in the jS~decay of 211Bi.
[Data from G. Neary, Proc. Roy. Soc. (London) A175, 71(1940)] (b) The energy spectrum
of the positron emitted in the /3+-decay of 13N. [Data by Siegbahn and Slatis, Ark. .4si.
Math. Fysik 32A, No. 9 (1945)]
to be neutral, to com ply w ith the law o f conservation o f charge, and o f v e ry small
mass, since the total mass is essentially accounted fo r b y the other observed par­
ticles. F o r these tw o reasons the new particle was called a neutrino. (T h is name
was proposed by E nrico Ferm i, and means “ the little neutron.”) I t is designated
by the sym bol v. A s we shall see in Section 9.5, it. has been found th at there are
tw o kinds o f neutral particles, alm ost identical, associated w ith /3-decav. One,
the neutrino, is em itted in /3+ -decay and electron capture, while the particle
em itted in /3“ -decay is called the antineutrino, and is designated b y P. H ow ever,
in this chapter w e shall refer in m ost cases to both particles b y the name “ neutrino.”

T h e neutrino is assumed to carry aw ay the energy and m om entum required to

restore the conservation o f both quantities. In the center-of-mass fram e o f refer­
ence the m om enta o f the three resulting particles m ust add to zero (F ig . 8 -1 2).
B ut there is an infinite number o f ways in which the total energy availab le can be
split am ong the three products, and this v e ry nicely explains the continuous energy
distribution o f the electrons o r positrons. T h erefo re processes (8.8), (8.9), and
(8.10) must be rew ritten in the follow in g form :

/3 -d eca y: z \ —♦ χ -j-j\ + e + v, (8.11)

/3+ -d eca y: I X —> z A Y + e + - f v, (8.12)

EC: j j x -f- c —» -f- v. (8.13)

So far we m ay say th at the neutrino is an interesting invention to save tw o con­

servation laws. B u t is there addition al confirm ation o f its existence? On the theo­
retical side, one can make a statistical analysis to determ ine how the energy re­
leased in the decay process is shared by the electron (o r the positron) and the
neutrino (see E xam p le 8.8). W h en this analysis is com pared w ith the experim ental
energy distribution o f the electrons (o r the positrons) and the neutrino, excellent
agreem ent is obtained, provided th at the rest mass o f the neutrino is v e ry small
(less than 10 mc). A c tu a lly the neutrino’s rest mass is considered to be zero
(m , = 0), and thus for a neutrino the energy-m om entum relation is E r = cpr.
On the experim ental side, it is easy to understand that, because o f its properties,
the neutrino should be v e ry difficult to observe, since it is insensible to the action
o f electric and m agnetic fields, and its v e ry small or zero rest mass does not allow
us to use mass measurem ents to observe its emission or capture. In fact the neu­
trino eluded direct observation until 195f5, when C. C ow an and F. R eines proved
beyond any d oubt that it existed. T h e ir experim ent is explained in E xam p le 8.0.
3Wt Nuclear processes

U n stable nuclei which lie ab ove the stab ility region in F ig. 7-1 can be considered
to have too m any neutrons (o r too few protons), and those which lie below can be
considered to have too m any protons (o r too few neutrons). Thus we should expect
that these nuclei would attain stab ility by ejectin g th eir excess neutrons or protons.
H ow ever, this is not w h at happens— unless the nucleus is in an excited state—
because not enough energy is availab le for such processes (recall T a b le 8 -2 ). W h a t
has been observed is th at electrons and positrons are em itted instead. T h erefore
we m ay assume that a nucleus attains stab ility when, in -decay, a neutron trans­
form s into a proton according to the scheme

n —> p + e " + v, (8.14)

while in β + -decay, a proton transforms into a neutron according to the scheme

p —> n + e + + v. (8.15)

In the case o f electron capture, the process is w ritten as

p -f~ e —►n v. (8.16)

In this w ay a nucleus m ay get rid o f its excess neutrons or protons w ithout actually
e m ittin g either o f these particles. T h is th eory o f j8-decay was proposed in 1934 by
Ferm i. E quations (8.14), (8.15), and (8.16) are com patible w ith Eqs. (8.11),
(8.12), and (8.13), and express in a m ore fundam ental w a y w hat happens in /J-
decay.
T h e ab ove processes allow us to infer another p rop erty o f the neutrino: its spin.
T h e neutron, proton, electron, and positron each h ave spin T herefore, in the
/J+ process, p —> n + e + + v, the angular m om entum on the left, in units o f h,
is J, while the angular m om entum o f n + e + m ust be £ ± J = I or 0, depending
on whether the neutron and the positron have their spins parallel or antiparallel.
T h u s the neutrino must have spin j , and be so oriented that the total spin or angu­
lar m om entum o f the three particles on the right add to j . In this w a y the law o f
conservation o f angular m om entum is also saved! T h e same logic applies to the
tw o other processes: (8.14) and (8.16). T h is also explains the observed changes o f
spin Δ / o f nuclei in /J-decay. I f the electron (o r positron) and the neutrino have
th eir spins parallel (trip le t states), then we h ave Δ / = ± 1 or 0, but if their spins
are an tiparallel (singlet states), then A l = 0.
Process (8.14) has been observed w ith free neutrons, since the reaction is exoergic.
In fact, the energy availab le is

Q = 931.48 [m„ — (m p + m e - f m f )] M e V = 0.7834 M e V .

Free neutrons decay according to E q. (8.14), w ith a half-life o f 13 min. T h is is one

o f the reasons w h y free neutrons do not exist. Free neutrons, sh ortly a fter they
are produced, are either captured by other nuclei or disintegrate into protons,
electrons, and neutrinos. On the oth er hand, processes (8.15) and (8.16) are endo-
ergic, as the student can v e rify by com puting the Q- value for each process; therefore
 Beta decay 365

free protons are stable to /3-decay, which accounts for the existence o f hydrogen.
Otherwise all hydrogen w ould have disappeared, either by capture o f the orb ita l
electron or b y disintegration o f the nuclear proton. Processes (8.1.5) and (8.16),
however, can occur in m ore com plex nuclei, when the required energy is supplied
by the difference in the binding energies o f the parent and the daughter nuclei.
H ow ever, neutrons bound in nuclei do not in general disintegrate spontaneously
because the presence o f the other nucleons m ay m ake the process en ergetically
impossible. F o r th a t reason m ost neutrons in nuclei are stable.
B eta decay illustrates tw o fundam ental facts o f physics. One is the im portance
o f conservation laws in an alyzing processes th at occur in nature. T h e other is the
variable nature o f the fundam ental particles. T h a t is, fundam ental particles, al­
though th ey have well-defined properties, are not perm anent structures, and one
particle m ay change into sets o f the others, w ith in the lim itations imposed by the
conservation laws. T h is is a radically new concept which was not con tem plated
either in classical or quantum mechanics. T h e interrelational character o f the
fundam ental particles opens an en tirely new v ista o f ideas about the structure o f
matter. In C hap ter 9 we shall explore this new situation in greater detail.
A com plete and satisfactory theory which can account for all the transform a­
tions am ong fundam ental particles has not y e t been developed. I t is assumed th at
processes such as (8.14), (8.15), (8.16), and others (which w ill be described in C h ap ­
ter 9) arc the result o f a differen t interaction, called the weak interaction. From the
analysis o f the half-lives and energy distribution o f /3-emitters, it has been estim ated
that the strength o f the w eak interaction is o f the order o f IO-13 when com pared
w ith that o f the strong or nuclear interaction, or about 10—11 when com pared w ith
the electrom agnetic interaction. A t present both strong and w eak interactions
p rovide challenging and excitin g areas o f research for the physicist, and, presum­
ably, th ey w ill continue to do so fo r m any years to come.

E X A M P L E 8.6. Analysis o f the Cowan-Reines neutrino-detection experiment.

S o lu tio n : When an antineutrino is captured by a proton, a neutron and a positron are

produced; that is,

p + P —* n + e +. (8.17)

This process o f antineutrino capture may be related to Eq. (8.15) in the same way as the
electron capture process, Eq. (8.16), is related to Eq. (8.15).
Nuclear reactors produce large numbers of /3“ -emitters, which are the products of
uranium fission (see Section 8.5), and thus nuclear reactors are copious sources of anti­
neutrinos. I f the antineutrinos from a reactor fall on hydrogenous material, process (8.17)
may take place.
The positron can be detected because it may collide with an electron, resulting in the
annihilation of both particles and the emission of 7-rays (Section 9.3), which can be easily
detected by means of scintillation counters. (See Appendix V II.) One can detect the
neutron by adding cadmium to the hydrogenous substance. Neutrons— after being slowed
down in their motion through the substance on account of collisions with other nuclei— are
captured by the cadmium nuclei with the emission of some Ύ-rays. This chain of events is
346 Nuclear processes

F Incident antineutrino

Scintillation
counter

Target tank
with cadmium

Scintillation
counter

F ig. 8-13. Schematic diagram of the neutrino detection experiment. The incoming
neutrino reacts with a proton at I. The ejected positron annihilates with an electron at
2 and the neutron is captured by a cadmium nucleus at 3.

depicted in Fig. 8-13. There is, of course, a delay of several microseconds between the
production of the 7-rays resulting from the electron-positron annihilation and the emission
of the 7-rays resulting from the capture of the neutron by cadmium. B y means of proper
electronic circuitry, the two sets of 7-rays are identified. An analysis of the experimental
results provides convincing evidence that the assumed chain of events has taken place
and that antineutrinos are actually coming from the reactor. Several other experiments
have confirmed the neutrino hypothesis. In the Cowan-Reines experiment, performed in
an underground room below one of the reactors at Savannah River, the antincutrino flux
was about 4 X IO10 cm-2 s-1 and the number of events registered was about three per
hour. I t is considered that the neutrino flux on the earth, coming mainly from the sun,
is about 4 X IO10 cm -2 s-1 .

E X A M P L E 8.7. Determination of the energy available for each of the β-decay processes
described by Eqs. (8.11), (8.12), and (8.13).

S o lu tio n : L e t us first consider β “ -decay, Eq. (8.11). Initially we have a nucleus of atomic
number Z and mass viz.. A t the end of the process we have a nucleus of atomic number
Z I and mass m z + i, plus an electron (mass mc) and a neutrino (zero mass). Thus the
energy available for the process is

Q s- = I ' » Z — ( ’» 2 + 1 + m .)]c 2 = ( v i z — Vl2 Jr I — vie)c 2.

Normally one uses the atomic masses M z instead of the nuclear masses, such that M z =
viz + Zm 9. Making this substitution, we get

Q f - = (M z - il/ z+ i)c2. (8.18)

For/3+-decay (Eq. 8.32), we have

 Bela decay 347

or, transforming into atomic masses,

Q i+ = ( M z ~ M z - i - 2m.)c2. (8.19)

Finally, for electron capture (Eq. 8.13),

Qeo = ( M z - M z - i ) c 2. (8.20)

Thus, whenever the atomic mass of a given atom is larger than that of either of the two
neighboring isobars, it will decay by either β ~ or electron capture. However, for β +
decay, the masses must differ by at least 2me (about 1.097X IO-3 amu or 1.022 M eV ). I t
is suggested that the student check these rules by looking atseveralgroups of isobars in
a table of nuclides. In writing these equations, we have neglected the effect due to the
binding energy of the electrons in the atoms. The energy Q is shared (as kinetic energy)
by the decay products. I f we neglect the recoil energy of the daughter nucleus, then Q
also gives the maximum kinetic energy of the electron or the positron in Eqs. (8.11)
and (8.12).
Let us illustrate these important rules with some examples. The nucleus 14C disin­
tegrates into 14N according to the scheme of Eq. (8.11), giving off an electron and a
neutrino. The masses of the atoms are M z ( 14C) = 14.007682 amu and M z + 1 ( 14N ) =
14.007515 amu. Therefore Eq. (8.18) gives Qg- = 0.000167 amu or 0.1556 M eV. The
observed maximum kinetic energy of the ejected electrons is 0.155 M eV, which is in
excellent agreement.
N ext let us consider the decay of 11C into 11B1 according to the scheme of Eq. (8.12).
The masses of the two atoms involved are M z ( 11C ) = 11.01492 amu and M z - i ( 11B) =
11.01279 amu. Thus their mass difference is 0.00213 amu or 1.985 M eV 1 which is larger
than 2»ie or 1.022 M eV. Therefore positron emission is possible with

Qi + = 1.985 M eV - 1.022 M eV = 0.963 M e V .

The measured maximum kinetic energy of the positrons observed in this decay is 0.96 M eV,
again in excellent agreement.
Finally we consider the decay of "Be, whose mass is M z ( 7Be) = 7.01915 amu. As
explained before, 7Be is found to decay into 7L i1whose mass is M z - 1 ( 7L i) = 7.01822 amu.
Their mass difference is 0.00093 amu or 0.866 M eV. This is less than 1.022 M eV, and
therefore positron emission is impossible. The decay therefore occurs via electron capture,
with Qec = 0.866 M eV.

E X A M P L E 8.8. Calculation of the shape of the energy spectrum in /3-decay.

S o lu tio n : Consider a large number of /3-radioactive nuclei. VVe observe the emitted
electrons (or positrons) during a certain time interval. Let us designate by dN the number
of electrons (or positrons) emitted with a kinetic energy between E ke and E ke 4- dEke.
Our purpose is to calculate dN/dEke, which is the number of electrons (or positrons) per
unit energy range. W e shall designate the kinetic energy available for the electron and
the neutrino by Eo which, if we neglect the recoil energy of the daughter nucleus, is prac­
tically equal to Q. Then Eo — E ke + E k,. Obviously Eo must be equal to the maximum
kinetic energy of the electron. When the kinetic energy of the electron falls within the
range dEke, that of the neutrino falls in the interval dEkr = — dEke. A fter the decay we
308 Nuclear processes (8.5

may treat the electron and the neutrino as free particles enclosed in a very large potential
box. Then dN /d Eu must be proportional to the number of electronic states per unit
energy range [that is, ge(E ke)] and the number of neutrino states per unit energy range
(Jy(E ky). That is, dN/dEu ~ ge(E u )g y(E ky). From Problem 2.11, we have g(p ) dp ~ p2 dp,
and therefore

g (E ) = g(p ) dp/dE ~ p 2 dp/dE.

For a neutrino having zero rest mass, the energy-momentum relation is p, = E ky/c.
IIcnce
Qy(E ky) ~ E2
ky = (E 0 - E u ) 2.

For an electron (which must be treated relativistically), the energy-momentum relation

is E u = c V m jfc2 + p2 — ViyC2■ Hence

g J E u ) ~ (E u V VieC2) ( E ky + ZmeP 2E u ) 1' 2.

Therefore we have

dN / d E ke = C (E u + wteC2) ( E l - f ZmeC2E u ) 1/2(£ o - E u ) 2, (8.21)

where C is a constant of proportionality which depends on several other factors involved

in the 0-decay, such as the atomic number Z of the decaying nucleus and the strength of
the weak interaction responsible for the decay. It also has some dependence on the
electron’s energy. Plotting dN/dEu against Eu , we may compare with the experimental
results shown in Fig. 8 -1 1(a) and (b). The agreement in general is rather satisfactory.
W e may note that Eq. (8.21) has been derived on the assumption that the neutrino has
a zero mass. However, if the rest mass had not been zero, we would have obtained a dif­
ferent result. Therefore the experimental confirmation of Eq. (8.21) is an indirect proof
that the neutrino has a negligible rest mass. Given the degree of accuracy of present ex­
periments, we can say that the rest mass of the neutrino must be less than O-OOlm0, and
therefore it can safely be taken as zero.

tt.S X u v iv a r Itv a v lio n s

W h en tw o nuclei, overcom ing th eir coulom b repulsion, com e v e ry close together

(w ith in the range o f the nuclear force), a rearrangem ent o f nucleons m ay occur.
T h is m ay result in a nuclear reaction, sim ilar to the rearrangem ent o f atom s in
reacting m olecules in a chemical reaction. N u c lea r reactions are usually produced
by bom barding a target nucleus (Λ/,·) w ith a nuclear projectile (m,·), in most cases
a nucleon (neutron or proton) or a ligh t nucleus such as a deuteron or an alpha
particle. H e a v ie r nuclei are not generally used because the electric repulsion be­
tween h e a v y nuclei requires a projectile w ith a large kinetic energy. Som etim es
photons are used as projectiles. M o s t o f the reactions result in the same particle,
or another particle (ni/) being ejected and a residual or final nucleus (.1//) being
le ft in its ground state or in an excited state. T h e reaction is designated by
the sym bols .!/,(w,·, where the initial and final nuclei are to the le ft and
8.5) Nuclear reactions 359

to the righ t o f the parentheses and the incom ing and ou tgoing ligh t particles are
inside the parentheses. F o r exam ple, when w e bom bard 1^ N w ith α -particles
(o r ^ H e), the result m ay be a proton (o r [ I I ) and a residual '| 0 nucleus. T h is
process m ay be w ritten in the form

14
IN + 2H e -►

or in the m ore ab b reviated notation mX (a, P ) 17O.

In general, when the energies o f the particles in vo lved are not too high, a
nuclear reaction supposedly occurs in tw o steps. F irs t: an incom ing particle or
projectile is captured, resulting in the form ation o f an intermediate or compound
nucleus which is in a highly excited state. In the second step, the com pound
nucleus m ay be de-excited, either b y emission o f the same incom ing particle or
by some other means. T h e ab ove exam ple can thus be w ritten in the form

th at the nucleus is in an excited state.

G enerally speaking, to a g iven first step in a nuclear reaction, there are several
modes o f de-excitation fo r the com pound nucleus. E ach m ode is called a “channel. ”
F o r exam ple, when 27A l is bom barded w ith protons, several products result, some
o f which arc listed below :

IJ S i + 7

i l N a -f- 3 JH + n

Som e nuclear reactions cannot be described by means o f the com pound nucleus
model. O ne exam ple is the strippin g reaction,

i| M g + 2H —* JH + i iM g ,

or f| M g (d , p ) 22 S- E xp erim en tal evidence indicates th at in this process, when

the deuteron comes v e ry close to the nucleus, the neutron is captured and the pro­
ton is repelled w ith ou t the form ation o f a com pound nucleus.
N u clea r reactions are essentially collision processes in which energy, m om entum ,
angular m om entum , number o f nucleons, and charge must be conserved; the m eth­
ods o f newtonian and relativistic mechanics are used to com pute some o f these
quantities (see Ap p en d ix I I ) . I f the incom ing and ou tgoing particles are the same,
the process is called scattering. Scatterin g is elastic if the nucleus is le ft in the same
state, so that kinetic energy is conserved, and inelastic if the nucleus is le ft in a
different state. In the inelastic case, the kinetic energy o f the ou tgoing particle
differs from the kinetic energy o f the incom ing particle.
350 Nuclear processes C8.5

T h e Q o f a nuclear reaction A/,(m,·, m f ) M / is given b y the expression

Q = [(M 1- + m,) - (M t + m/)]c2. (8 .22)

In the ab ove equation atom ic masses arc alw ays used. I f Q is positive, the reaction
occurs at all values o f the kinetic energy o f the incom ing p ro jectile; but if Q is neg­
ative, v ii m ust h a ve a t least a threshold kinetic energy to produce the reaction.
A s w e shall see in E xam ple 9.8, the threshold kinetic energy o f the incom in g par­
ticle in the L -fra m e o f reference is

, M i -I- m,- + mj -I- Mj

if the particles m ust be treated rela tivistically. H o w ever, if the particles can be
treated n on relativistically, so that Q is sm all and m / M / can be replaced in the
num erator b y Λ/,■- f m,·, the threshold kinetic en ergy o f the p ro jectile in the L -
fram e o f reference is

T h is is the expression used in most cases.

In some cases the p rojectile is captured but no new particle is em itted. Instead,
a gam m a ra y (o r p h oton ) is em itted, whose energy depends on several factors,
such as the state o f the resulting nucleus and the binding energy plus the kinetic
energy o f the captured particle. A n exam ple o f a capture reaction is 27A l(n , 7 ) 28A l.
A n oth er is the capture o f a neutron b y hydrogen in the reaction 'I I ( n , 7 ) 2H ; the
resulting atom is deuterium. T h e reverse process m ay also occur: a nucleus m ay
absorb a photon or 7-ray whose energy is sufficient for a particle to be ejected.
T h is process, which is equ ivalent to the photoelectric effect in atoms, is called a
pholonuclear reaction. E xam ples are 25M g (7 , p ) 24N a and 21I(7, n )'H .
A nuclear reaction m ay be described in term s of a cross section. T h e concept
o f cross section was introduced in Sections 1.9 and 7.8 fo r certain processes. Of
course, for each particular nuclear reaction, there is one cross section, which is ex­
pressed as a function o f the en ergy o f the p rojectile or incom ing particle. Cross
sections are defined experim entally in the follow in g w ay. Suppose th at a sam ple
o f thickness A x (w here Ax is sm all) and area Λ , containing n, target nuclei per unit
volum e, is exposed to a current density nav o f incom ing particles (o f ty p e a ) per
unit area and unit tim e, where na is the number of incom ing particles per unit
volu m e and v th eir v e lo c ity . G iv e n that N lj ou tgoing particles (o f ty p e b) are ob­
served leavin g the sam ple per unit tim e, the cross section for the reaction (a, b) is

(8.23)
σ (α’ ^ (n uv )(n ,A Δ χ )

T h is definition coincides w ith E q. (7.10), since n tA A x is the total number o f target

nuclei and thus N h Zfn lA A x ) gives the total flux per unit tim e o f ou tgoing particles
8.5) Nuclear reactions 351

per target nucleus. W e note th a t Ni, is expressed in s_ l , th at nav is expressed in

in -3 ms-1 or m ~ 2 s—1, th at n tA Ax is a unitless number, and th at σ is expressed
in m 2 as in previous cases. M o s t cross sections are o f the order o f R 2 ~ IO-28 in2,
where R is the nuclear radius. T h e qu a n tity IO-28 in 2 is called a bam , ab b revi­
ated b, as m entioned in Section 7.3. I t is a unit com m only used for expressing
cross sections o f nuclear processes. Λ subm ultiple is the m illibarn, mb, equal to
IO-31 m 2.
F o r a g iven incom ing particle a, there m ay result several d ifferent ou tgoin g par­
ticles b, b ', b " , corresponding to the several reaction channels, each with its own
cross section σ (α , b), σ (α , b '), etc. T h e total reaction cross section fo r p article a is
then
σ (α ) = σ (α , 6) + <τ(α, b ') + σ (α , I!>") + · · ·

T h e partial and total m acroscopic cross sections o f a given sam ple are defined by

Z ab — η ,σ(α . b)
and (8.24)
Σ„ = η ,σ (α ),

and both are expressed in m _ l .

T h e cross section for each nuclear reaction depends on the energy o f the in­
com ing particle. In m any nuclear reactions the cross sections exhibit v e ry pro­
nounced peaks called resonances, corresponding to energies a t which the particular
reaction is m ore favored or probable. These resonances are closely related to the
energy levels o f the com pound nucleus. Figure 8 -1 4 (a ) and (b ) shows the total
and capture cross sections for neutrons in alum inum in terms o f the neutron energy.
Figure 8—14(c) gives the cross section, in arb itra ry units, for the nuclear reaction
37C l(p , n )37A as a function o f the proton energy. F rom the analysis o f such curves,
we can obtain extensive inform ation about nuclear structure and energy states.
In m any cases the nucleus which results from a nuclear reaction is unstable or
radioactive. In fact, it is through nuclear reactions that the artificia lly rad ioactive
nuclei are form ed. A rtificia l ra d io a c tiv ity was discovered by F. J olio t and I. Curie
in 1934, while th ey were stu dying nuclear reactions produced by bom barding light
elements w ith α -part.icles. One o f the reactions they observed was

1Eb + Il-Ie [ 1I N ] * - » ' I N + n.

T h e nucleus 13N is unstable and decays according to the scheme

‘I n -» 1I c + e+ +

A n oth er interesting series o f reactions are those resulting from com bined neu­
tron capture and /8-decay o f the uranium isotopes, producing new nuclei with
Z = 93 (neptunium ), Z = 94 (plutonium ), Z = 95 (am ericium ), and so on up to
Z = 100. T h e partial chain o f reactions is shown in F ig. 8-15, where each hori­
zontal arrow represents a neutron capture and each vertical arrow a /3-decay.
352 Nuclear processes C8.5
Total cross sections, b

Neutron energy, keV

cross section, mb
Capture

Neutron energy, keV

units
section, arbitrary
Cross

Proton energy, keV

8.5) Nuclear reactions 353

240 242 244 246 248 ' 250 ‘ 252 ' 254

M juss miniher, .I

F ig. 8-13. Nuclear reaction sequences for production of heavy nuclides by slow neutron
irradiation of 230Pu.

E X A M P L E 8.9. Attenuation of a beam of particles of type a as a function of the dis­

tance x traversed in a target.

Solution: Designating by I = n„v, the incoming current density of particles of type a

falling on a layer of thickness Ax, we have from Eqs. (8.23) and (8.24) that

Ι Σ Ax = Nb/Λ

gives the number of particles removed per unit area and per unit time from the incoming
beam; in other words, it gives the decrease in the current density of the projectiles, which
must be designated by —A l since A l is negative. So we may write

A l = — ΙΣ Ax. (8.25)

If the thickness Ax is very small, we may write instead

d l = — ΙΣ dx or d l / I = - Σ dx.

Integrating, and designating the incoming particle flux for x = 0 by I o, we obtain

/ = I 0e~ -‘ . (8.20)

We may use this equation to determine Σ after measuring Io and I. Once we know Σ, we
obtain σ by using Eq. (8.24).

Fig. 8-14. (a) The total and (b ) the capture cross section of aluminum for neutrons
as a function of neutron energy. [Data from R. Henkel and H. Barschall, Phys. Rev. 80,
145 (1950)] (c) Cross section for the reaction 37Cl(p, n) 37A as a function of proton
energy. [Data from Schoenfeld, Duborg, Preston, and Goodman, Phys. Rev. 83, 873
(1952))
355 Nuclear processes (,8.5

E X A M P L E 8.10. Discovery of the neutron.

Solution: An interesting and historical application of the conservation laws in nuclear

processes is the story of the discovery of the neutron. In 1930 Bothe and Becker observed
that when they bombarded boron and beryllium with α -particles, a highly penetrating
radiation was produced. This radiation was not composed of charged particles because
it was not affected by electric or magnetic fields. For that reason they thought that the
radiation consisted of high-energy 7-rays, and they wrote the reaction as

Slie + oHe -> [ ‘ «C l* - 'iiC + 7. (8.27)

The Q of this reaction is 10.4 M eV. Since the kinetic energy of the α-particle is about
5 M eV 1 the total energy available is 14 M eV in the cm frame of reference. This energy
must be shared by the '«C atom and the 7-photon. Thus the 7-rays should have an
energy slightly less than 14 M eV. From absorption measurements it was estimated that
the photon energy should be about 7 M eV. Tw o years later (1932) Curie and Joliot ob­
served that when the radiation from the above reaction passed through a hydrogeneous
material, highly energetic protons were produced, with a maximum energy of about
7.5 M e V . The natural interpretation was to assume that the protons had been knocked
out by collision with 7-photons produced in the above reaction, resulting in a (7, p)
nuclear Compton effect. The most energetic protons result from a head-on collision in
which the photons recoil or are deflected 180°. Given that E r and pr = E r/c are the
energy and momentum of the incident photon, E r and p'r = E r/c those of the recoil
photon, and Eic and p = V 2m p/s’* those of the proton (which may be treated nonrela-
tivistically), the conservation of energy and momentum give

Er = E1
r + Es, E r/c = - E'r/c+ V 2 m pE t .

from which we may get

E r = i ( E t + V 2 (m ,

Inserting the maximum value of Eu, 7.5 M eV , and recalling that mvc- is about 938 M eV,
we then get E r ~ 64 M eV. This value of the 7-ray photons is much larger than the
energy available from the reaction, given above as 14 M eV , or that deduced from absorp­
tion measurements. What is worse, considering the effect of the products of the Be-He
reaction on other substances, we obtain other values of E r , in some cases as high as
90 M eV . Therefore we can obtain no consistent results for E r from Eq. (8.27), com­
patible with energy and momentum conservation.
In 1932 the British physicist J. Chadwick showed that all these difficulties disappeared
and the conservation laws were restored if. instead of 7-rays, neutral particles were
emitted, having a mass close to that of protons. These neutral particles were called neu­
trons, and the process can now be written as

4Be + e lle - l ‘ 2C]* - 'oC + !,n. (8.28)

Chadwick made careful measurements of the kinetic energy of protons and nitrogen atoms
knocked out by the neutrons when they were passing through a substance containing
hydrogen and nitrogen, respectively. This allowed the mass of the neutron to be calculated,
8.5) Xuclear reactions 355

resulting in a value between 1.005 and I.OOS amu, which is consistent with the energies
involved in the above, reaction. Later on, more precise measurements yielded
Vin = 1.008665 amu.
Chadwick’s experiments were the foundation of our present model of the nucleus, a
model which assumes that the nucleus is composed of protons and neutrons. Prior to
that time scientists considered nuclei as being composed of protons and electrons (.I
protons and .1 — Z electrons, or a total of 2.1 — Z particles). But that assumption
resulted in insurmountable difficulties: electrons were too big compared with the nuclear
radius, their magnetic moments were IO3 times larger than nuclear magnetic moments,
and their presence inside a nucleus made it impossible to account for the observed values
of the nuclear spins. Thus the timely recognition of the neutron was more than welcome.

E X A M P L E 8.11. A sheet of gold 0.3 mm thick is exposed to a slow neutron current

density of IO7 neutrons cm- 2 s-1 . The capture cross section of 107Au for thermal neu­
trons is 94 X IO-28 m2. The density of gold is 19.3 X IOi kg m -3 and its atomic mass
i s 197.2 amu. Find the number of nuclei of 1 0 8 A u formed per second and per cm 2 of the

sheet, according to the reaction 197Aufn1T I 108Au.

Solution: Let us designate the capture cross section of 107Au for thermal neutrons by
σ(η, T) and the number of atoms of gold per unit volume by nAu. Then the macroscopic
cross section for neutron capture, according to Eq. (8.24), is Σ = « Αι,σ(η, 7 ). Given that
I 0 is the incident neutron current density, the number of neutrons that have not been
captured after a distance x, according to Eq. (8.26), is I = I Oe- -L The number of neu­
trons that have been captured in the distance x is thus

I0 - I = /o(l - e~-z).

This is equal to the number of 108Au nuclei formed. In our case,

_________ 19.3 X IO3 kg m-3_______________________ μ —3

” Au 197.2 amu X 1.66 X 10~27 kg a m u '1

is the number of 197Au atoms per m3. Thus Σ = nAucr(n, I ) = 562 m- 1 . Setting
x = 0.3 mm = 3 X IO-4 m, we have S r = 0.1686 and e~tx = 0.845. Therefore

I0 - I = IO7 n cm-2 s- l ( l - 0.845) = 1.55 X IO0 Ocm- 2 S-1 .

This gives the number of neutrons absorbed and of 198Au atoms formed per cm2 and per
second.

E X A M P L E 8.12. Determination of the energy levels of 28Si by use of the nuclear reac­
tion 27Al(p , a ) 24 M g and its inverse, 24M g fa 1p )27Al.

Solution: The compound nucleus of the reaction 27Alfp, a ) 24M g Ls 28Si1 so that we
may write

27A l + 1H - » [28Si]* - » 4H e + 24Mg.

I t is expected that the cross section for this reaction will show marked peaks (i.e., reso­
nances) w'hen the total energy in the C-frame of reference of the system 27A l + 1H
minus the rest-mass energy of 28Si coincides with the energy required to excite 28Si to
356 Nuclear processes (,8.5

I
p
11.588 *
lit,.
-'7A l + '! I

t 9 .990
10
2
4M r + 4M c
-9
I I
I I

Kinetic energy o f incoming particle plus target

nucleus in the C-framc o f reference

(It)

F ig. 8-16. Evidence for the compound-nucleus concept by use of the reactions
27A I(p ,o ()24M g and 24M g fa 1 p )27A l The compound nucleus is 28Si. (a) Energy rela­
tions, (b) cross section for both reactions. |Data from Kaufmann1Goldberg, Koester1and
Mooring, Pliys. Rcv., 88, 673 (1952)]

one of its stationary states. This energy is

[ M ( 27A l) + »ip - JI/(28Si)]c2 + E kp = (1 1 .5 8 8 + Ekl,) M e V 1

where AJp is the total kinetic energy of the system (p, 27A l) in the C-frame. Once the
compound nucleus is formed, it may break into the system 24M g + a. The 24M g may
be in its ground state or in an excited state; the state of the 24M g nucleus determines the
kinetic energy of the α-particle and of the 7-rays observed when the 24M g nucleus proceeds
to its ground state. The inverse reaction, that is,

24M g + 4H e -> [28Si]4 —> Ή + 27A l1

produces a 28Si nucleus with an excitation energy given by

[.U (24M g) + m (JHe) - .U (28Si)Jc2 + E ka = (9.990 + E ka) M c V 1

8.6) Nuclear fission 357

where Eka is now the total kinetic energy of the system (a, 24M g) in the C-frame. The
different energy relations are sketched in Fig. 8-16(a).
From our discussion it is clear that the cross sections for the reaction 27Alfp, a )24M g
and its inverse, 24M g fa 1p )27Al, must show the same set of resonances. However, for
each resonance the kinetic energy of the system (a, 24M g) is uniformly larger than the
kinetic energy of the system (p, 27A l) by the amount (11.588 — 9.990) M eV = 1.598
M eV when the energies are referred to the respective C-frames. This conclusion is con­
firmed by the experimental results shown in Fig. 8-16(b), which gives the cross sections
for protons with energies from 1.1 to 1.8 M eV and for α-particles with energies from
2.7 to 3.4 M eV . The result constitutes a satisfying verification of the compound nucleus
concept, and serves to show the origin of resonances in nuclear reactions. The energy
levels of 28Si, in the energy region considered, can be determined from the energies of the
peaks shown in the figure.

0 .6 ' X u e lv a r JFittnion
A n im portant nuclear process is fission. I t consists in the division o f a h eavy nu­
cleus, such as uranium or thorium, into tw o fragm ents o f com parable sizes. Fission
as a natural process is v e ry rare ( 238U is believed to fission spontaneously w ith a
half-life o f app roxim ately 1 0 '0 years). T h e usual m ethod o f producing fission arti­
ficially is to excite the nucleus. T h e threshold or m inim um a c tivatio n energy re­
quired fo r fission o f a heavy nucleus is from 4 to 6 M e V . One o f the m ost effective
means o f inducing fission is by neutron capture. T h e binding energy o f the cap­
tured neutron is, in som e cases, enough to excite the nucleus a b o v e the threshold
energy, so that division into tw o fragm ents takes place. T h is is, for example, the
case o f the nucleus 2||U , which undergoes fission after capturing a slow (o r therm al)
neutron. T h e process m ay be expressed by the equation

23D2
5 U - F n - * [2g|U ]* - » X + Y .

For other cases, in order for fission to take place, the neutrons must have some
kinetic energy— o f the order o f I M e V — in addition to the binding energy. T h is
is what occurs with 2g|U, which fissions on ly after capturing a fast neutron. T h e
reason for this differen t b ehavior lies in some details o f the structure o f the different
nuclei related to the pairing term in the mass form ula given in E q. (7.1‘2 ). The
nucleus 2Q8U is even-odd, w ith 143 neutrons, and when a neutron is captured, an
even-even nucleus, 2|2U , is formed. T h e captured neutron is paired w ith the last
odd neutron o f 2|2U , releasing the additional pairing energy δ ~ 0.57 M e V . On
the other hand, 2g lU is an even-even nucleus, w ith 146 neutrons, all paired, and
when a neutron is captured, an even-odd nucleus, 2g 2U, results, with no extra
pairing energy available. F o r the same reason 2g|Pu, w ith 145 neutrons, undergoes
fission b y slow neutron capture. T a b le 8 -3 gives the excitation energy o f some
nuclei resulting from neutron capture and their fission activation en ergy; from
this inform ation it is possible to deduce which nuclei are fissionable by thermal
neutrons.
358 Nuclear processes C8.6
T A B L E 8—3 K issionahility o f H eavy N u clei w ith T h e r m a l
N e u tro n s

Target Compound Excitation Threshold

nucleus nucleus energy, M eV energy, M eV

23SU I231U] 6.6 4.6

235 p; 6.4 5.3
[236U]
238 ( ; 4.9 5.5
I239U]
232Th [233Th] 5.1 6.5
23lPa I232Pa] 5.4 5.0
237Np (238Np) 5.0 4.2
23aPu [240Pu] 6.4 4.0

T A B L E 8—1 T h re sh old E nergies fo r

Bhotofission

Photofission
Nuclide threshold,
M eV

238 u 5.08 ± 0 .1 5
235t .
5.31 ± 0.25
233 j -
5.18 ± 0.27
239Pu 5.31 ± 0.27
232Th 5.40 ± 0.22

A nucleus m ay also be excited enough to suffer fission by absorbing 7-rays o f

energy equal to or larger than the threshold energy required for fission. T h is proc­
ess is called photofission. T h e threshold energies for photofission are g iven in
T a b le 8-4 for some nuclei.

O
O
F ig . 8-17. Deformation of a nucleus
according to the excitation energy. (a) (b) (c)
O (d)

F igu re 8-17 depicts the supposed mechanism o f nuclear fission. C onsider a

nucleus whose equilibrium shape is spherical, as in Fig. 8 -1 7 (a ). I f p roperly ex­
cited, it m a y experience collective vibrations, as explained in Section 7.10. W h en
the excitation energy is low, the oscillations about the spherical shape are small,
so th at at its m axim um deform ation the nucleus adopts the ellipsoidal shape shown
8.6) Nuclear fission 359

N 1,

F ig. 8 -1 8 . Potential energy function for a nucleus under deformation.

in F ig. S—17 (b ). O n c e the excitation energy has been released in the form o f 7-rays,
the nucleus r e tu r n s t o the equilibrium shape. T h e process has therefore been a
ra d iative neutron cap tu re. W h en the excitation energy is larger, the nucleus is
deform ed more, a s in F ig . 8 -1 7 (c ). E v en in this case there is some prob ab ility th at
it m ay return to t h e original shape a fte r de-excitation by 7 -ray emission. B u t if
the excitation e n e r g y is large enough, the deform ation m ay be so large th at the
electrical rep u lsio n b etw een the tw o halves is larger than the short-range nuclear
interaction, and t h e r e is a greater prob ab ility that the nucleus, instead o f return­
ing to the s p h e r ic a l shape by releasing 7-rays, deform s m ore and m ore until it
divides into tw o fr a g m e n t s — as indicated in Fig. 8 -1 7 (d )— resulting in fission.
F igu re 8-18 s h o w s schem atically the potential energy o f a nucleus versus its
deform ation. F o r d e fo rm a tio n s sm aller than a certain critical value, designated I )
in the figure, the n u c le a r forces dom inate the electrical forces and the potential
energy increases w i t h th e deform ation, resulting in the curve A B . T h is is the region
o f stable os c illa tio n s . F o r deform ations larger than D , the electrical forces dom inate
the nuclear forces, a n d the poten tial energy decreases w ith further deform ation,
resulting in curve B C , which corresponds to the division into tw o fragm ents; these
fragm ents fly a p a r t because o f their coulom b repulsion. I f E 0 refers te the ground
state o f the n u cleu s, t h e fission threshold energy is E/. T h is curve should be taken
on ly in a q u a lit a t iv e sense.
I f the nucleus i s in it ia lly in a state w ith energy less than th at a t B, such as
E 0 or E , it u n d e r g o e s oscillations w ith out fission. I t is prevented from spontaneous
fission b y the p o t e n t i a l barrier. T h e nucleus m ay, how ever, tunnel through the
poten tial barrier, r e s u lt in g in spontaneous fission. T h e p rob a b ility o f tunneling is
extrem ely low w h e n t h e nucleus is in the ground state, so th at spontaneous fission
is a rather im p r o b a b le even t. H ow ever, the pen etrab ility o f the barrier increases
360 Muclear processes (8.6

w ith the excitation energy o f the nucleus, m aking fission m ore probable. I f the
nucleus has an excitation energy larger than E i , it ob viou sly undergoes fission.
T h erefo re fission by neutron capture w ill occur if the binding energy plus the
kinetic energy o f the captured neutron are enough to take the nucleus ov e r the
poten tial barrier. As we said before, if the binding energy alone is enough, slow
neutron fission occurs. F or 218U 1 the height, o f the potential barrier is about 5.3
M e V ; thus 5.3 M e V is the critical energy required to produce the fission o f 235U
b y neutron capture. I t is im portant to note, however, that there is not a
single threshold energy or a unique critical deform ation ; these quantities depend
on the excitation m ode o f the nucleus and the initial state o f the nucleus.
T h e capture o f a neutron does not necessarily lead to fission even if the energy
is available, because (as explained p reviou sly ) before the nucleus has tim e to split,
it m ay relc.asc its excitation energy in the form o f 7-rays, resulting in ra d ia tiv e
capture instead o f fission. T h erefore, when neutron capture takes place, tw o com ­
p eting processes enter into p lay: rad iative capture (n, 7 ) and fission (n, f). Each
o f flic- tw o processes is characterized by its ow n cross section— designated by
σ (η , 7 ) and σ (η , f), resp ectively— which depends on the energy o f the neutron.
T h e values o f these cross sections are given in T a b le 8 -5 fo r neutrons h a vin g a
v e lo c ity o f 2200 m s - 1 , which corresponds to the average v e lo c ity o f thermal
neutrons at room tem perature. T h e last column lists the average number o f
neutrons released per fission.

T A B L E 8-5 Properties o f S om e F issionable M a te ria ls fo r

T h e r m a l N e u tro n s

Nucleus σ(η, f), barns σ(η, 7 ), barns V

2 33 LT 525 53 2.51

2 3 5 jj 2.44
577 101

239Pu 742 286 2.89

Fission is not a sym m etric process; in general the tw o fragm ents have unequal
mass numbers. T h e m ost probable division is into fragm ents w ith mass numbers
around 95 and 135, as shown in Fig. 8-19, which gives the fission y ield o f 233U,
235U, and 239Pu for therm al neutrons. T h is can also be seen in F ig. 7-1, where
the rad ioactive nuclides above the s ta b ility region are particularly abundant in
the regions around A = 90 and /I = 135, associated w ith N = 50 and N = 82,
respectively. T h e reason for this asym m etry seems to be the tendency o f a h eavy
nucleus to split into fragm ents h a vin g closed neutron shells around the m agic
numbers 50 and 82, respectively.
T w o properties o f fission m ake it a v e ry im p o rtan t process for practical applica­
tions: One is th at neutrons are released in fission and the other is that energy is
released in fission.
8.6) Nuclear fission 361

Mass number Mass number

(a) (b)

Fig. 8-19. (a) Thermal and fast fission yield of 235U. (b) Thermal fission yield of 233U
and 239Pu. [Data from S. KatcofT, Nucleonics 16, No. 4, 78 (April 1958)]

W e can see th at neutrons are released in fission by exam ining the stab ility region
in F ig. 7-1. F o r the heaviest nuclei, such as uranium, the ratio o f neutrons to
protons is N / Z ~ 1.55. Th is, o f course, w ill be app roxim ately the ratio for the
resulting fragm ents. H o w ever, from the same figure w e see that for medium-mass
stable nuclei the ratio is N / Z ~ 1.30. T h is means th at the resulting fragm ents
have too m any neutrons, and thus lie ab ove the stab ility region. T h erefore they
are β ~ ■
-radioactive. In fact, uranium fission is one o f the m ethods o f producing
β ~ -radioactive isotopes. H o w ever, the neutron excess is so large that a few neutrons
are released at the tim e o f fission. T h e average number o f neutrons released per
fission (designated as v) is given in T a b le 8 -5 for some nuclides, assuming that
fission is induced b y slow neutrons.
T h a t energy is released in nuclear fission m ay be seen from the binding energy
per nucleon, represented in Fig. 7-5. F o r a h eavy nucleus, the binding energy is
about 7.5 M e V per nucleon, but fo r medium-mass nuclei, corresponding to the
tw o fragm ents, it is about 8.4 .McV per nucleon, resulting in an increase o f binding
energy per nucleon o f abou t 0.9 M e V 1 o r a total o f about 200 M e V for all nucleons
in a uranium nucleus. This, then, is the order o f m agnitude o f the energy liberated
in the fission o f a uranium atom. T h e energy released appears as kinetic energy o f
the fragm ents, o f the released neutrons, and o f the disintegration products (th a t
is, electrons, photons, and neutrinos) resulting from the d-deeay o f the rad ioactive
362 P1
JucIear processes (8.6

fragm ents. Since the neutrinos em itted in the /3-decay (and a fe w photons as w e ll)
n orm ally escape from the m aterial in which fission takes place, on ly about 180 M e V
per atom can be retained, an energy still considerably larger than the energy lib­
erated in a chem ical reaction (which is o f the order o f 3 to 10 e V per atom ).
F o r exam ple, the energy released in the fission o f 235U is distributed, on the
average, as follow s:

K in e tic energy o f fragm ents 1G7 M e V

K in e tic energy o f fission neutrons .■>
E n ergy o f 7-rays (radiated at the tim e o f fission) 7
E n e rgy o f /3_ -decay electrons
E n ergy o f 7-decay o f fragm ents
E n e rgy o f β ~ -decay neutrinos
T o ta l energy 200 M e V

T h e exact energy distribution varies, o f course, from one case to another.

T h e fact th at for each neutron absorbed in order to produce one fission, m ore than
tw o new neutrons are em itted (on the avera ge) suggests the possibility o f a chain
reaction. T h a t is, if things are arranged in such a w ay that, after each fission, at
least one o f the new neutrons produces another fission, and o f the neutrons released
in this fission, again at least one produces a fission, and so on, then a self-sustaining
process or chain reaction results. (C h ain reactions are v e ry com mon in chem istry.
C om bustion is a chain reaction. B urning requires th at a m olecule have a certain
excitation energy so that it can com bine w ith an oxygen molecule. B u t once the
first m olecules are excited and com bine w ith oxygen, the energy liberated is enough
to excite m ore molecules o f the fuel, and burning results.) I f in each stage o f the
process more than one neutron per fission produces a new fission, the number of
fissions increases exponentially and a d ivergen t chain reaction results. T h is is
what happens in an atom ic bomb. B ut if, on the average, on ly one neutron of
each fission produces a new fission, a steady chain reaction is m aintained under
controlled conditions. T h is is what happens in a nuclear reactor.
In fast nuclear reactors the neutrons arc used a t the same energies ( I to 2 M e V )
a t which they are released in the fission process. But in lhennal nuclear reactors
the neutrons arc first slowed down b y allow ing them to collide w ith the atom s o f
som e other substance, called a moderator, until they com e to therm al equilibrium
w ith the substance. T h e neutrons are then called thermal. T h e m oderator must
be a substance which has small mass number and a small neutron capture cross
section. W a ter, heavy water, and graphite are the substances m ost used as
moderators.
T h e energy released in a nuclear reactor is extracted by means o f a circulating
fluid called a coolant. In pow er reactors this energy is used for heating or for the
generation o f electric power. In research reactors the neutrons are used for d if­
ferent kinds o f experim ents, or for isotope production.

E X A M P L E 8.13. Determination of the energy released when a neutron is captured by

235U and by 238U and the feasibility of fission of 23sU and 238U by thermal neutrons.

*
8.7) Nuclear fusion 363

S o lu tio n : The Q for the capture reaction of a neutron by an atom of mass number Λ is

Q = (Μ λ + m„ - .V .i+ i)c 2 = 931.48(37,, + m„ - Μ λ + ύ M eV,

where the masses in the second expression must be expressed in amu, and all refer to
atomic masses.
Considering the case of 235U 1 which becomes 230U after capturing a neutron, we have
AZa(235U) = 235.1170 amu and .l/a + ι ( 230U) = 236.1191 amu. Using mn = 1.0090
amu, we find that Q = 6.-13 M eV. On the other hand, the potential barrier of 230U
for fission is about 5.3 M eV. Therefore the excitation energy of 230U formed as a
result of the capture of a neutron by 235U is larger than the height of the potential
barrier for fission. W e conclude then that the 238U nucleus resulting from the neutron
capture by 235U undergoes fission even if the neutron is so slow that it contributes a
negligible kinetic energy.
Considering the case of 238I 11 which becomes 239U after capturing a neutron, we have
AZa(238U) = 238.1249 amu and M λ +1 ( 239U) = 239.1287 amu. Thus the Q of the cap­
ture reaction is 4.85 M eV 1 which is smaller than the height of the fission barrier of 239U
by about 0.6 M cV. Therefore, unless the captured neutron has sufficient kinetic energy
to make up for the energy required, fission is not produced. Experimentally it is found
that the minimum laboratory kinetic energy of the neutrons must be about I M eV to
fission 238U.

//. 7 \ u r l f a r F u sion
A process which is the reverse o f nuclear fission is nuclear fusion . I t consists in the
coalescence o f tw o colliding nuclei into a larger nucleus. Because o f the coulom b
repulsion between nuclei, they must have a certain kinetic energy to overcom e the
coulom b poten tial barrier and g et close enough so that nuclear forces produce the
necessary consolidating action. T h is problem is not present in nuclear fission be­
cause the neutron does not have an electric charge, and thus can approach the
nucleus even if its k inetic energy is v e ry sm all or p ractically zero. Since the cou­
lom b barrier increases w ith atom ic number, nuclear fusion occurs at reasonable
kinetic energies on ly for ve ry light nuclei w ith low atom ic number or nuclear charge.
W e shall now estim ate the kinetic energy required to place tw o nuclei o f atom ic
numbers Z 1 and Z 2 in contact. L e t r in the electric poten tial energy o f tw o nuclei
( E p = Z \Z2e~/A7Γ€/)>') be equal to the sum o f the nuclear radii, or about IO -14 m.
T h en w e obtain E p ~ 2.4 X I O - 14Z 1Z 2 J = 1.5 X IO5Z 1Z 2 e V = O -Io Z 1Z 2 M e V .
T h is gives the height o f the poten tial barrier and therefore the m inim um initial
relative kinetic energy o f the tw o nuclei necessary for fusion to occur. I f the col­
liding particles do not have a kinetic energy equal to or larger than E p, fusion
cannot occur. H ow ever, at energies sligh tly low er than E p there is some p rob ab ility
o f fusion by penetration o f the coulom b barrier. T h e average kinetic energy o f a
system o f particles havin g a tem perature T is o f the order o f k T , or about

8.6 X IO- 5 T eV,

where T is in absolute degrees. T h u s the energy o f IO5 e V corresponds to a tem pera­

ture o f about IO9 0K , which is much higher than the tem peratures believed to exist
a t the center o f the sun. E ven so, fusion is one o f the m ost im portant processes
364 Nuclear processes (8.7

occurring in the sun, and is its main source o f energy. T h e fusion takes place
am ong the re la tiv ely small number o f light nuclei which have energies w ell above
the average energy at the sun’s tem perature.
W e conclude that, if nuclear fusion o f a large number o f nuclei is to take place,
it is necessary fo r the reacting nuclei to be a t tem peratures much higher than those
generated by even the m ost exoergic chemical reaction. T h e extrem e tem perature
creates a problem o f containm ent o f the reacting particles, since no known m aterial
can sustain such tem perature. A lso, a t these tem peratures, the nuclei are stripped
o f all their surrounding electrons (because o f collisions) and the substance con­
sists o f a neutral m ixture o f p ositively charged nuclei and negative electrons called
a plasma. C ontainm ent has been attem p ted by means of m agnetic fields. Also,
when the inten sity o f the m agnetic fields is rap idly increased, the plasma is com ­
pressed adiab atically and its tem perature increases until fusion begins. S everal
ingenious devices have been built th at perform these tw o functions o f containm ent
and heating.
A s we m ay see by referring to Fig. 7-6, energy is liberated in nuclear fusion o f
light nuclei (A < 20). W hen tw o ligh t nuclei coalesce in to a heavier one, the bind­
ing energy o f the product nucleus is greater than the sum o f the binding energies of
the tw o lighter nuclei, and this results in a liberation o f energy. I f the conditions
are appropriate, the energy liberated in fusion is enough to excite other nuclei, and
a chain reaction results. T h e chain reaction becomes a nuclear explosion by a
mechanism sim ilar to a chemical explosion, but in this case the explosion is due to
nuclear instead o f electrical forces. T h e chain reaction m ay also occur under con­
trolled conditions, although no fu lly satisfactory fusion reactor has yet been built.
T h e sim plest fusion react ion is the capture o f a neutron by a proton (o r hydrogen
nucleus) to form a deuteron:

} H + n — ?H + 2.226 M e V . (8.29)

T h e great ad van tage o f this reaction is th at there is no electrical potential barrier

to be overcom e. A s will be seen in the next section, scientists assume th a t this
fusion reaction played an im portant role in the ea rly stages o f the evolution o f the
universe. A t present, however, this fusion reaction is rela tiv ely unim portant due
to the lack o f a sufficient number o f free neutrons. N evertheless, reaction (8.29)
occurs when neutrons from a nuclear reactor diffuse through a hydrogeneous sub­
stance, such as w ater or paraffin.
A n o th er sim ple fusion reaction is that between tw o protons. Since a diproton
nucleus does not exist, the process is accom panied by the conversion o f one o f the
protons into a neutron a t the expense o f the binding energy o f the resulting deu­
teron, and the emission o f a positron and a neutrino. T h a t is,

H + } I I - > ?H -I- e + + v + 1.35 M e V . (8.30)

A th ird im portant fusion reaction is th at between hydrogen and deuterium, re­

sulting in a tritium nucleus:

jH + * H - » iH + e + + v + 4.6 M e V . (8.31)
8.7) Nuclear fusion 365

A fusion reaction which has a large cross section and which liberates a great
am ount o f en ergy is th at between deuterium and tritiu m :

TH + ?H - » |He + n + 17.6 M e V . (8.32)

A n oth er possible deuterium fusion reaction, in v o lvin g 3I I e 1 is

I H + I H e -> !H e + } H + 18.3 M e V . (8.33)

H ow ever, since tritium and 3H e are n o t so readily available, th e fusion o f tw o

deuterium nuclei or deuterons is o f m ore practical im portance. T h is hasthe addi­
tional ad vantage o f using on ly one class
o f nuclei. T h e resulting products m ay be
d ifferent; tw o possibilities occur with
about th e same p ro b ab ility:

jjH e + η + 3.2 M e V
/
i H + ?H
\
? II + } H + 4.2 M e V
(8.34)

T h e cross sections for processes (8.32)

and (8.34) are shown in F ig. 8-20.

F ig. 8-20. Cross sections of the deuteron-

deuteron and deuteron-triton fusion re­
actions as a function of deuteron energy.
[Data from A. Bishop, Project Sherwood,
Reading, Mass.: Addison-Wesley, 1958]

A lth ou gh the energy released in a single fusion reaction is much less than th at
released in a single fission reaction, the energy per unit mass is larger (because
deuterium is a v e ry light fuel). F o r the deuterium -deuterium fusion reaction, the
energy is about 2 X IO m J per kilogram o f fuel. T h is is m ore than double the value
for uranium fission. Due to the rela tiv e abundance o f deuterium (abou t one deute­
rium atom fo r about 7000 hydrogen atom s), and the rela tiv ely low cost o f extracting
deuterium from w ater (ab ou t 300 per gram ), scientists predict th at— once con­
trol led-fusion devices becom e practical— the fusion process will provide an alm ost
unlim ited source o f energy.
Fusion reactions are the source o f the energy o f the sun and the other stars.
One o f the m ost im portant fusion processes is the Bethe or carbon cycle, which is
366 Nuclear processes (8.7

equ ivalen t to the fusion o f four protons into a helium nucleus. T h e cycle occurs
in the follow in g steps:

In + 12o C - > * ? N

' I n - » 1JJc + e+ + v
}H + 1GC - » 1JN

Ih + 'I n - » 1I o (83o)
1Io - > ‘ ?N + e + + V

Iη + 1I n -* 1I c + !H e .

A d d in g all the reactions and canceling com m on terms, we have

4 iH - > |H e + 2e+ + 2v + 26.7 M e V . (8.36)

The net energy lib erated in the process is 26.7 M e V , or about 6.6 X IO 14 J per kg
o f JH consumed. N o te that the carbon atom is a sort o f catalyzer, since it is re­
generated a t the end o f the cycle. T h e tim e required for a carbon atom to go
through this cycle in the sun is about 6 X IOe years. T h e cycle is shown schemat­
ically in Fig. 8-21.

Fig. 8-21. The carbon cycle.

A n oth er fusion reaction in stars is the Critchfield or prolon -prolon cycle, which
consists o f the fo llo w in g steps:

Jh + J ii -» ? h + e+ + *
Jh + TH — IH e (8.37)

I l I e + |He - » |He + 2 }H .

P ro p erly com bined, these reactions also y ield E q. (8.36). T h e period o f the proton-
proton cycle in the sun is about 3 X IO0 years. T h e cycle is shown schem atically
in F ig . 8-22.
A s explained in the next section, astrophysicists b elieve th at the proton-proton
cycle presently predom inates ov e r the carbon cycle in the sun and stars o f sim ilar
structure, but th at in m any youn ger stars the situation is the reverse and the
carbon cycle is m ore im portant. In older stars that have much higher tem pera­
tures, other types o f fusion reactions are also b elieved to take place.
8.8) The origin of the elements 367

I t is estim ated that process (8.36) is occurring in the sun a t the rate o f
5.64 X 1 0 " kg per second o f hydrogen fusing into helium, w ith a release o f
3.7 X IO25 W . O f this, o n ly about 1.8 X IO 14 W falls on the earth, m ostly in the
form o f electrom agnetic radiation; however, this is still IO5 tim es greater than all
the industrial pow er generated on the earth.

S M T h v O rig in o f th v E iv m v n t*
W e shall now consider the interesting and im portant question o f the origin o f the
elements. B y origin we m ean the mechanism b y which the present, com position o f
the universe was achieved, assuming the existence o f certain prim eval m atter.
T h e statem ents w e shall m ake arc m erely speculative, since there is on ly incom ­
plete evidence available.
One o f the clues w e use for our speculation is the rela tive abundance in the
universe o f the different chem ical elements, as shown in F ig. 8-23, and the other is
their isotopic com position. A s w e can see from the figure, hydrogen is the most
abundant, follow ed b y helium. A fte r the sudden drop in abundance corresponding
to lithium , beryllium , and boron, the abundance follow s a regularly decreasing
trend, levelin g off for Z > 35 or A > 80, but w ith some pronounced maxima,
especially for iron and neighboring nuclides. T h e elem ents stop a t Z = 92, since
the am ount o f existing nuclei w ith Z > 92 is essentially zero, although they have
been produced a rtificia lly in the laboratory up to Z = 103. A s to isotopic com ­
position, the lighter elements are richer in those stable isotopes w ith low er neutron
content, while the heavier nuclei are richer in isotopes w ith higher neutron content.
Also, e v en -A nuclei are m ore abundant than odd-.4 nuclei. A n oth er interesting
feature is th at no nuclei w ith A = 5 or 8 are found in nature.
T h e relative abundance and isotopic com position have been found to be the
same not on ly in samples taken from various parts and depths o f the earth’s crust
but also in samples taken from m eteorites which h ave fallen on the earth from
outer space. T h is constant com position suggests that, at least in our galaxy, the
elem ents w ere all form ed b y app roxim ately the same process. T h e “ zero tim e ”
368 Xuclear processes (8.8

F ig. 8-23. Cosmic abundance of the elements. [Data from H. Urey and H. Brown,
Rlnjs. Rev. 88, 248 ( 1952) J

o f the process is estim ated to have occurred a t about (8 ± 2) X IO9 years ago.
T h is figure was obtained b y tak in g into account several astrophysical considera­
tions, such as the v e lo c ity o f receding galaxies, and by an alyzing the natural radio­
active chains.
M a n y theories h a v e been advanced to explain this general com position o f the
universe, but no single th eory is com pletely satisfactory. T h e m ost acceptable
th eory at this tim e (attrib u ta b le to Fow ler, H oy le, B urbridge, and Greenstein,
am on g others) postulates that the elem ents are synthesized in stars under v aryin g
conditions. T h e sequence o f even ts contem plated by this theory is as follow s:
Suppose th at in itially (i.e., a t “zero tim e ") there is a v e ry large mass o f gaseous
hydrogen (w ith , perhaps, som e free neutrons). Due to statistical fluctuations and
g ravita tion al interaction, some o f this hydrogen m ay condense in to clusters, or
stars, reaching a density o f the order o f IO5 kg m - 3 . In the process o f condensation
there is a transform ation o f gravitation al potential energy into kinetic energy,
resulting in an increase o f tem perature (to about IO7 ° K ) of the gas. A t such
tem peratures the proton-proton cycle o f E q . (8.37) is possible. H elium thus be­
gins to be form ed. I t is possible that, as by-product reactions o f the proton -
proton cycle, rela tiv ely small quantities o f nuclei w ith higher atom ic mass m ay
be form ed. F o r exam ple, 7Li is produced by the process

OlIe -j- 2H e —* JBe -F Ύ, ^Be -F c 3Ei -F v.

8.8) The origin of Ihe elements 369

P a rt o f the lithium reverts back to helium through the reaction

I L i + {Η — |He + !H e .

O ther fusion reactions, such as (8.29), (8.31), and (8.33), m ay also tak e place, but
in much less amount.
Since helium is more m assive than hydrogen, the helium nuclei produced in the
proton-proton cycle are carried to the center (o r core) o f the star by gravita tion al
action. T h e density at the core m ay then becom e as high as IO8 kg m ~ 3. The
resultant gain in kinetic energy o f the helium nuclei a t the core increases the core
tem perature (u p to values o f IO8 ° K ). T h e surface tem perature o f a star in whose
interior a large qu a n tity o f helium nuclei has accum ulated increases and its color
consequently changes. T h e increase in tem perature and density o f helium nuclei
at the core increases the possibility for the production o f fB e by the helium fusion
reaction
! H e + ! H e - » fB e ,

which is follow ed, in about IO -16 s, b y the decay process

fB e - > !H e + !H e .

H o w ever, due to the rela tiv ely large helium concentration, it is possible for another
helium nucleus to be captured before this d ecay occurs, resulting in the reaction

fB e + ! H e - » ‘ iC .

A lte rn a tive ly , the interm ediate products in the proton-proton chain f H and |He
m ay be captured by the beryllium , form in g 1IJB and 1^C 1 respectively, although
in much sm aller am ounts th an 1§C. A lso m an y other less-probable reactions can
take place which result in other light elements.
T h e chain o f events just described explains how the gaps a t A = δ and 8 can
be bypassed. T h is mechanism also makes the scarcity o f lithium , beryllium , and
boron understandable, as well as explaining the rela tiv ely great abundance o f ‘ |C.
B j' the same process o f helium capture, the production o f successively m ore m assive
nuclei such as 'fO , fJjNe, anc^ others is possible. T h e on ly lim itation to helium
capture is the am ount o f energy required by the !H e nuclei to overcom e the cou­
lom b repulsion o f the h eavier nucleus. F igu re 8-24 is a schem atic representation
o f the series o f events proposed by this th eory o f helium capture (o r burning).

F ig. 8-24. The helium burning process.

370 Nuclear processes 8.8
(.

W ith the production o f heavier nuclei great quantities o f helium are used up
and a further g ravita tion al contraction o f the star should take place, leading to
core densities o f the order o f IO9 kg m -3 (w ith a corresponding increase in the
kinetic energy o f the nuclei and a core tem perature which approaches 10° ° K ).
U n der such conditions o f v e ry high density and extrem e tem perature, other nuclear
reactions are possible which m ay produce nuclei o f higher mass number, up to the
iron group (ab ou t A = CO), but not heavier, due to the energy lim itations men­
tioned above. F ree neutrons m ay be produced in som e instances through (a, n)
reactions, such as

1I C + !H e —> 19O + n,

's O -f- 2 lie —» io N e -(- n,

I oK e + jH e —* Ia M g I n.

T hese neutrons, togeth er with som e o f the original (o r prim eval) neutrons which
have not decayed into protons, arc availab le for exten din g the production o f
nuclei to higher mass numbers— that is, nuclei beyond the iron group— by neutron
capture rath er than by the capture o f charged particles. In m any instances neu­
tron capture reactions result in /3~-decay (as w e have seen, every tim e a nucleus
acquires too m any neutrons, it decays by electron emission). T h e resultant nu­
cleus has a higher atom ic number a fte r the /3“ -decay and the chain can thus ad­
vance tow ard higher Z-valucs. O f course, as tim e passes, the number o f free
neutrons decreases. T h is then is an explanation for the fact th at the h eavier elem ents
are rela tiv ely less abundant since the production o f the heavier elem ents is alm ost
entirely dependent on neutron capture.
Since the in itial “ firin g-u p” o f a star is based on a statistical fluctuation, the
stars in the universe cannot all be expected to follo w the same sequence a t the
sam e rate, and the stars are presently in differen t stages o f evolution. T h e sun
itself is still m ostly in the first stage o f evolu tio n ; its com position is assumed to be
81.70% hydrogen, 18.17% helium, and 0.07% fo r the rest o f the elements. Stars
In which the proton-proton cycle presently appears to be the dom inan t process
are called m ain sequence stars. T h ose stars in which a t present it appears th a t the
m ost im portant process is helium -burning are called red (jiants because o f their
color. In m an y stars the three stages o f nucleosynthesis proposed by this theory
are assumed to be tak in g place sim ultaneously, w ith hydrogen-burning occurring
a t the surface, helium reactions prevailin g a t an interm ed iate (and h o tte r) layer,
and h eavy elem ents being produced in the much h o tter core o f the star. Stars that
have e v o lv e d in the w ay predicted by this th eo ry are called first-generation stars.
In som e instances instabilities which arise during the evolu tion and aging o f a
star m ay result in the ejection o f som e o f the m aterial from its in terior into inter­
stellar space, where it mixes w ith uncondensed hydrogen and the dust o f outer
space. C ondensation o f some o f this m ixture a t som e later tim e results in second­
hand later) generation stars. I t is in these youn ger stars th at the carbon cycle,
E q . (8.3.5), plays an im portant role.
 Problems 371

T h e theory o f the origin o f the elements is much m ore com plex than our lim ited
review can possibly indicate, but w e cannot explore this m atter in greater detail
here. W h a t w e h ave said should be enough to m ake the student appreciate the
ideas explored in this interesting, challenging, and creative area o f physics.

ltvferencvH

1. “ Resource Letter N R - I on Nuclear Reactions," T. Griffy, Am. J . Phys. 35, 297 (1967)
2. “ The Discovery of Nuclear Fission,” II. Graetzer, .1m. ./. Phys. 32, 9 (1964)
3. “ A Study of the Discovery of Fission,” E. Sparberg, .lm. J . Phys. 32, 2 (1964)
4. “ Nuclear Fission,” R. Leachman, Sci. Am., August 1965, page 49
5. “Thermonuclear Reactions,” G. Thomson, .lm . J. Phys. 28, 221 (I960)
6. “ Recent Developments in Controlled Fusion,” A. Bishop, Physics Today, March 1964,
page 19
7. “ The Origin of the Elements” by W . A. Fowler and “ The Structure of Nuclei” by
V. Weisskopf in The Scientific Endeavor. N ew Y ork : Rockefeller Institute Press, 1965
8. Structure of Matter, W . Finkelnburg. N ew Y ork : Academic Press, 1964, Chapter V,
Sections 9-19
9. Principles of Modern Physics, R. Leighton. N ew Y ork: M cGraw-Hill, 1959, Chap­
ters 16 and 17
10. Nuclear Physics, I. Kaplan. Reading, Mass.: Addison-Wesley, 1963
11. Introduction to the Atomic Nucleus, J. Cuninghame. Amsterdam: Elsevier, 1964
12. Radioactivity and Its Measurement, W . Mann and S. Garfinkel. Princeton, N.J.:
Van Nostrand, Momentum Books, 1966
13. .1 Source Iiook in Physics, W. Magie. Cambridge, Mass.: Harvard LTniversity Press
(1963); page 613 (Becquerel); page 617 (P. and M. S. Curie)

P ro b lvm H

8.1 The half-life of 90Sr is 28 years.
Determine: (a) the disintegration constant
for " S r , (b) the activity of I mg of " S r
in curies and as nuclei per second, (c) the
time for the I mg to reduce to 250/ig,
(d) the activity at this later time.
8.2 A freshly prepared sample of a radio­
active material, which decays to a stable
nuclide, has its activity measured every
20 seconds. The following activity (in
yCi) is measured starting at ( = Os: 410;
190; 90; 43; 20; 9.6; 4.5; 2.15; 1.00; 0.48;
0.23. (a) Plot the natural logarithm of the
activity against the time, (b) Find the dis­
integration constant and the half-life of the
sample, (c) How many radioactive nuclei
were present in the sample at / = 0 s?
8.3 A material is composed of two differ­
ent radioactive substances having half-lives
equal to 2 hrs and 20 mill., respectively.
Initially there is one mCi of the first sub­
stance and 9 mCi of the second, (a) Using
semilogarithniic paper, plot, as functions
of time, the activity of each substance and
also of the whole material, (b) A t what
time is the total activity one mCi? (c) A t
372 Nuclear processes
what time is the activity of the short-lived
substance 1 % of the long-lived substance?
8.4 The activity of a material is measured
every 30 s and the following values (in
counts per minute) are found: 1167; 264;
111; 67; 48.3; 37.1; 30.0; 24.6; 20.9; 18.1;
15.7; 13.9; 12.3; 11.1; 9.84; 8.85; 7.83; 7.02;
6.26; 5.60; 5.00. (a) Plot the logarithm of
the activity versus time, (b) Determine
how many radioactive substances are pres­
ent and compute the half-life and disinte­
gration constant of each. [H in t: First
subtract the activity of the longest-lived
substance by extending the tail of the curve
in a straight, line back to zero time. Plot
the remaining activity and repeat the proc­
ess until a straight line, corresponding to
the shortest-lived substance, remains.]
8.5 Show that the average life, T livct of a
radioactive substance is given by
[°
Tavc = - ^ - / t (IN = r ·
No J x ο X 140Cc. Also calculate the recoil energy of
8.6 Solve Example 8.2, assuming that
initially there are N o nuclei of the radio­
active substance. Consider particularly
the cases in which N o < g/λ and ΛΓο > g/\.
8.7 Referring to Example 8.3, show that
the number of nuclei of material C (a stable
nuclide), as a function of time, is given by
N e = - - A° —
c Xe - Xa
X IX e d - < Γ λ·4') - X a d - e _X/i')].
8.8 Referring to Fig. 8-4, show that the
time at which the number of nuclei of sub­
stance B is maximum is equal to
In (X b /X.D
X b — X.i
8.9 A steel piston ring with a mass of 25 g
is irradiated in a nuclear reactor until its
activity is 9.0 mCi (due to the nuclide 59Fe
which has a half-life of 3.90 X 10Gs). T w o
days later the piston ring is installed in a
test engine. A fter a ten-day test run, the
crankcase oil is drained and studied for
activity due to o9Fe. Investigation shows
an average activity of 9.8 X IO2 disintegra­
tions per second for a 200-cm3 sample of
the oil. Compute the mass of iron worn off
the piston ring, given that the crankcase
has a capacity of 7.6 liters.
8.10 The activity of carbon found in living
specimens is 0.007 ^Ci per kilogram, due to
the 14C present. The charcoal taken from
the fire pit of an Indian campsite has an
activity of 0.0048 μΟί kg-1 . The half-life of
14C is 5760 years. Calculate the year the
campsite was last used.
8.11 Plot the logarithm of the disintegra­
tion constant versus the energy for the a-
deeays listed in Table 8-1. Show that the
points lie approximately along a straight
line, so that log X = a,E„ + 6. Determine
a and 6 for best fit.
8.12 Calculate the energy of the «-p arti­
cle released by 144N d when it decays to
the daughter nucleus. The rest masses
are 143.9100 amu and 139.9054 amu,
respectively.
8.13 An elastic collision between an a-
partide and a nucleus of unknown mass
is observed in a cloud chamber. T h e a-
particle is deflected 55° from its original
direction, while the nucleus leaves a track
which makes an angle of 35° with the in­
cident direction. What is the mass of the
nucleus?
8.14 The range, R, of α -particles in air
and the α -partiele energies E are related
by the empirical relation R — 0.318F3/2 m,
where E is in M eV. (a) For the a-particle
energies shown in Fig. 8- 8 , determine the
range of the α-particles emitted when 211Bi
decays, (b) The α-decay of 212Po is ob­
served in a cloud chamber, and four
ranges— 11.2, 11.0, 9.57, and 8.51cm—
are measured. Calculate the energies of
these α-part icles. (See Fig. 8-9.)
8.15 The α -dccay spectrum from 220Ra
has a triplet structure, with a-particle

energies of 4.777, 4.593, and 4.342 M e V .
Assuming that the daughter nuclide 222Iin
is produced with a ground and two excited
states, draw the energy-level diagram and
show the 7-ray emission associated with
the transition.
8.16 Show the possible modes of decay for
40K , which has a rest mass of 39.9610 amu.
Compute the energy available for each
possible process.
8.17 Show from mass measurements that
64Cu may decay by /S+- and /8- -emission,
or electron capture. Experimentally, we
know that 04Cu has a half-life of 12.8 hours
with 39% β~, 19% 0 + and 42% EC.
Compute the energy available for each of
the three processes.
8.18 (a) Show that 7Be decays by elec­
tron capture. Its rest mass is 7.016929 amu. with a kinetic energy E k (in the A-frame of
(b) Compute the energy and the momentum reference) against a nucleus of mass M t
of the neutrino and the daughter 7Li
nucleus.
8.19 Calculate the maximum energy for
the electron in the /3“ -decay of 3II.
8.20 When 14O decays by /3+-emission, the
daughter 14N nuclide is almost always in
an excited state (> 9 9 % ). From the experi­
mental data which are given in Fig. S-10(b)
and from the fact that 14N has a rest mass
of 14.003071 amu, calculate the mass of
14O.
8.21 Plot the masses of isobars with
A = 40, 64, and 134 against Z. Show
the possible chains of /3-decays and the
most stable nuclides. Join the upper and
lower values, starting from the stable
nuclides, and note that, the connecting
lines are parabolas. Measure the mass
separation between the two lines and show
that it is consistent with the odd-even
correction term of Eq. (7.11),
δ = ± 3 4 .4 _3/4 M eV.
8.22 Plot the energy distribution of elec­
trons in /3-decay, as given by Eq. (8.21),
for Eo = 1.24 M eV. Compare with
Fig. 8- 11(b).
Problems 373
8.23 Complete the following nuclear re­
action equations, substituting the correct
nuclide or particle wherever an X appears:
(a) S A l ( n , « ) X ; (b) i|P(7, n).Y;
(c) |JP(d, p).Y; (d) 1IC(JY1Cr)IBe;
(e) 1IB fY 1 A-)?Be; (f) 1IIln (U 1Y)JY;
(g) ϋ Ν Ϊ(ρ , n ) X ; (h) 2?Co(n, JY)|?Co.
8.24 The mass defect of a nucleus is defined
as Δ = A — M , where A is the mass num­
ber and M the nuclear mass in amu.
Express the Q-value for 0 ~ - and β +-decay
and the reaction M iOm , m /)M f, in terms
of the value of the mass defect Δ for each
of the particles involved. [H in t: See
Examples 8.4 and 8.5.]
8.25 A particle with mass m, is projected
initially at rest in the laboratory. Show
that (a) the total kinetic energy of the sys­
tem in the C-frame is E kM J ( M i + m,),
(b) the total energy available for the reac­
tion M Am i, m /)M f isQ-f- E kM iZ iM i + m,·),
and (c) the threshold kinetic energy of m,
in the A-frame of reference (when Q is
negative) is —Q(.U, + m,)/.!/,. Assume
that the particles can be treated non-
relativistically.
8.26 For the photonuclear reaction
24M gfY 1n) 23Mg,
determine the threshold energy of the
photon. The rest masses of the parent and
product nuclides are 23.9S504 and 22.99412
amu, respectively.
8.27 A certain accelerating machine can
accelerate singly charged particles to an
energy of 2 M eV and doubly charged
particles to 4 M eV. W hat reactions may
be observed when 12C is bombarded by
protons, deuterons, and α-particles from
this machine?
8.28 When 7Li is bombarded by 0.70-
M eV protons, two α-particles are produced,
each with 9.0 M cV kinetic energy, (a) Cal­
374 Nuclear processes
culate the Q of the reaction, (b) Calculate
the difference between the total kinetic
energy of the α-particles and the kinetic
energy of the initial proton in the Λ-frame.
8.29 The rest mass of 13AI is 26.98154 amu.
Find the mass of the product nuclei for the
following reactions:
(a) 27A lfn 17 ) 28Al, Q = 7.722
(b) 27AK p 1a ) 24Mg, Q = 1.594
(c) 27A l(K 1P )28A I1 Q = 5.497
(d ) 27A K (K a )25M g 1 Q = 6.693
8.30 Show that the Q of a nuclear reaction
Jl/,·(»!,·, m ,)M , is given by
Q = AVIl + - E iI - (m./.l/.)],
where E i is the kinetic energy of the inci­
dent particle and E/ is the kinetic energy
of those «I/ particles observed at an angle
of 90° with respect to the direction of the
incident particle.
8.31 For the following reactions, find the
threshold energy of the projectile in the L -
frame, assuming the target nucleus is at
rest: (a) I 4N (a , p) 17O; (b) luO in1a) 13C.
8.32 A sample of natural silicon is bom­
barded by a 2.0-M eV beam of deuterons.
(a) W rite all the possible reactions in
which either a proton or an α-particle is
the ejected particle, (b) In each case, find
the kinetic energy of the ejected particle
in the C-frame and its maximum and min­
imum kinetic energy in the C-frame.
8.33 A t relatively low (thermal) energies
the neutron capture cross section for many
substances is inversely proportional to the
velocity of the neutron. This is called the
1/e law. IIo w should the plot of the loga­
rithm of the thermal-neutron cross section
against the kinetic energy of the bombard­
ing neutron appear?
8.34 Given that the capture cross section
of 197Au for neutrons follows the 1/e law
(see Problem 8.33), and that its capture
cross section for thermal neutrons
(0.025 eV ) is 99 b, find the absorption
cross section of 197Au for 1.0-eV neu­
trons. W hat thickness of a gold foil will
absorb 20% of a beam of 1.0-eV neutrons?
8.35 A tantalum foil 0.02 cm thick whose
density is 1.66 X IO4 kg m ~ 3 is irradiated
for 2 hr in a beam of thermal neutrons of
flux IO16N in-2 s_1. The nucleus 182T a 1
with a half-life of 114 days, is formed as a
result of the reaction 181T atn 17) 182Ta.
M eV ;
Immediately after irradiation, the foil has
M eV ;
an activity of 1.23 X IO7 disintegrations
M eV;
per second per cm2. Find (a) the-number
M eV. of 182T a nuclei formed, (b) the cross sec­
tion for the (n, 7) reaction producing 182Ta.
8.36 A borated-steel sheet which is used as
a control rod in a nuclear reactor is 1.59 mm
thick and contains 2% boron by weight.
The absorption cross sections of iron and
boron for energetic neutrons are 2.5 b and
755 b, respectively, (a) Find the macro­
scopic absorption cross sections of each of
these elements in the borated-steel sheet.
(b) What fraction of a neutron beam is
absorbed in passing through this sheet?
(c) Calculate the macroscopic cross section
of the sheet if the boron content is increased
to 3% . (The density of boron is 2.5 X IO3
kg in-3 , and that of steel is 1.9 X IO3
kg nr-3 .)
8.37 A beam of 370-keV neutrons is di­
rected at a sheet of aluminum foil 0.1 mm
thick. Given that the capture cross section
of aluminum for neutrons of that energy is
3 mb, see Fig. 8-14(b), determine the frac­
tion of neutrons captured. The density of
aluminum is 2.70 X IO3 kg m -3 .
8.38 Repeat Problem 8.37 for a beam of
neutrons whose energy is about 45 keV.
Figure 8—14(b) shows a peak in the capture
cross section of about 18 mb at 45 keV.
8.39 The capture cross section of 10B for
thermal neutrons is about 4000 b. How
thick a layer of 10B is required to ab­
sorb 99% of an incident beam of thermal
neutrons? (Density of boron: 2.5 X IO3
kg m -3 .)
8.40 Show that 6Li is stable to fission by
analyzing all the possible ways in which
it might split (for example, 6Li —* d + a,

etc.). Similarly show that 5L i and 5H e
are unstable to fission.
8.41 In the photofission of 235U into noKr,
142Ba1 and three neutrons, calculate, from
the mass differences, the total energy re­
leased. Compare this energy with the
initial coulomb repulsion energy of the
two charged fragments, assuming that they
are just touching when fission occurs.
8.42 Calculate the energy required to
split a 4He nucleus into: (a) 3H and p;
(b) 3He and n. Explain the difference be­ Eq. (8.35). It starts with the capture of
tween these energies in terms of the prop­
erties of nuclear forces.
8.43 Show that the energy released in the
fission of uranium (185 M eV per atom) is
equivalent to 8.3 X IO13 J k g -1 . A t what sultant fusion of four protons into an a-
rate should uranium fission so that I M W
of power is generated? How long would it
take for I kg of uranium to be used up,
given that it is continuously generating
I M W of power?
8.44 It may be shown that spontaneous
fission will occur if 02A/03Z 2 ~ 25A/Z2
is less than unity, where 0 2 and 0 3 are
coefficients in the Weiszacker formula,
Eq. (7.11). Calculate this ratio for 132Xe,
142Ce, 200H g1 235U 1 and 255Fm.
8.45 Compute the excitation energy of
the nucleus produced when a neutron is
captured by each of the following nuclei:
232T h 1 233T h 1 233U 1 234U 1 239Pu1 and
240Pu. Which of these nuclei would
we expect to be fissionable by thermal
neutrons?
8.46 (a) What must be the average tem­
perature of a deuterium plasma in order
for fusion to take place? [H in t: W e may
estimate this by calculating the coulomb
repulsion energy between deuterons when
they are within the range of the nuclear
Problems 375
force, ~ IO-15 m.j (b) Calculatetheenergy
released in the fusion of two deuterium
nuclei into an a-particle.
8.47 What energy is released in the fusion
process 3 4H e —* 12C? This process occurs
in the second stage of nucleosynthesis in
stars. Determine the power generated by
this process in a star in which 5 X IO9 kg
of 4He are fused in 12C per second.
8.48 The nitrogen cycle is a fusion process
similar to the carbon cycle given in
a photon by a 14N nucleus. After succes­
sive reactions, in which the nuclides 15O 1
15N 1 10O1 17F 1 and 17O are involved, the
14N nucleus is regenerated, with the re­
particle. (a) Write the different steps of
the nitrogen cycle in detail, (b) What is
the total energy released in the nitrogen
cycle?
8.49 Show that, if the energy produced
by the sun is to be accounted for, its mass
must decrease at the rate of 4.6 X IO9
k g s -1 . How much time must pass for
the mass of the sun to decrease by 1 %
(mass of the sun = 1.98 X IO30 kg)?
8.50 How long would it take for the length
of the year to increase by one second due to
the loss of mass of the sun by radiation?
(Sec preceding problem.) Recall that the
square of the period of the motion of a
planet around the sun is inversely propor­
tional to the mass of the sun.
8.51 Assuming that the rate at which
hydrogen is fused into helium in the sun
since its beginning has remained the same,
show that the age of the sun must be of
the order of 2 X IO10 years. The estimated
age of the sun, based 011 other calculations,
is of the order of IO11 years.
 9
FUNDAMENTAL
PARTICLES

9.1 Introdudion
9.2 Particle Genealogy
9.3 Particles and Anliparticles
9A Particle Instability
9.5 The Conservation Laws
9 .6 Invariance, Sym m etry, and Conservation Laws
9.7 Resonances
9 .8 What Is a Fundamental Particle?
9.1) Introduction 377

9.1 I n i r <nlnet io n

W e shall conclude our discussion o f the structure o f m atter by briefly considering

the building blocks o f which all m atter is composed. These building blocks are the
fundamental or elementary particles, to which w e have referred on several occasions.
So far in this text we have encountered the follow ing particles: proton, neutron,
electron, positron, and neutrino. T o this list w e m ay add the photon, which is also
considered to be a fundam ental particle. T h e first three particles seem to be the
on ly ones needed to explain the structure o f atom s and nuclei. T h e positron ap­
pears to be unnecessary fo r th at purpose; its existence, how ever, confirms the
v a lid ity o f the relativistic and quantal ideas when th ey are applied to the realm
o f fundam ental particles (th is requires a m athem atical analysis beyond the level
o f this book). A p p a ren tly the neutrino is required to satisfy three basic laws:
the laws o f conservation o f energy, m om entum , and angular m omentum. A n d the
photon is the carrier o f the electrom agnetic interaction between charged particles.
T h a t is, the electrom agnetic interaction o f tw o charges is described as an exchange
o f photons (see Section 1.6).
M a y we expect m ore fundam ental particles to exist? Reasoning b y analogy,
we m ay expect th at the strong interaction between protons and neutrons also
requires th at there be a carrier particle, which w e m ay call a pion (a fte r the name
ττ-meson origin ally given to it). A n d the g ra vita tion al interaction between tw o
masses should require that there be another carrier particle, which we call a yraviton.
Sim ilarly, the weak interaction should be associated w ith a carrier particle, called
the W -p article. Indeed, pions have been observed in cosmic rays and are produced
in large quantities in high-energy accelerators, but no experim ental evidence for
the g raviton or the W -p article has y e t been found.
In the last 30 years m any other particles (som etim es predicted, other times
unsuspected) have been observed. Som e o f them seem to behave in rather strange
w ays and no reason for their existence has y e t been found. M o re than 30 rela tively
stable particles (m ean lives longer than IO -10 s) have been identified. A b o u t 50
extrem ely short-lived particles (m ean lives shorter than IO -21 s), som etim es called
resonances, h ave also been identified. These discoveries have been m ade possible
by the construction o f v e ry high-energy accelerators which produce particles w ith
an energy o f several G eV , as well as b y the refinem ent in techniques o f observing
particles. These techniques include cloud, bubble, and spark chambers and photo­
graphic emulsions (in all o f which the charged particles leave visible tracks), d if­
ferent kinds o f detectors— such as G eigcr-M u ller, scintillation, and C erenkov
counters— as w ell as rather sophisticated electronic circuitry. W e shall not enter
here into a discussion o f these experim ental techniques; however, some o f the
apparatus for particle detection is described in Ap p en d ix V I I .
Because the m athem atical com plexities o f the th eory o f fundam ental particles
go qu ite beyond the elem entary introduction to quantum mechanics g ive n in
C hapter 2, our discussion o f the subject in the follow in g pages w ill be m ostly quali­
tative and descriptive.
378 Fundamental particles (9.2

T A B L E 9-1 F u n d a m e n ta l Particles

Rest
Rest Charge Spin
mass A n ti­
Particle Symbol energy, (in units (in units
(in units particle
M eV of e) of h)
of me)

Massless bosons
Graviton (?) K O 0 0 2 g
Photon 7 O 0 0 I 7

Leptons (fermions)
Neutrino V O 0 0 i P
Eleetron C- I 0.511 —I e+
Muon P~ 206.8 105.7 —I i P+

Mesons (bosons)
Pion TT+ 273.9 140 +1 0 7T —
TT0 264.2 135 0 0 TT0

Kaon K+ 966.7 494 +1 0 K-

K0 974.6 498 0 0 K0
»)-meson 9° 1074 549 0 0 V0

Baryons (fermions)
Nucleons
proton P+ 1836.2 938.3 +1 i P-
neutron n0 1838.7 939.6 0 2 h°
Hyperons
lambda A0 2184 1116 0 i A0
sigma 2+ 2327 1189 +1 2~
1 2°
2° 2333 1192 0 2
Σ- 2342 1197 —I i 2+
1 go
xi H0 2573 1315 0 2
2585 1321 —I
omega Ω- 3276 1674 —I § H+

9 .2 ! ‘ a r l i f l v H vnvoU u jtf
T a b le 9-1 presents a list o f known (circa 19G7) particles (excluding the resonances),
and also gives some o f their properties. F igu re 9-1 shows a tim e table for d iscovery
o f these particles. T h e three basic quantities used to id e n tify the particles are
mass, charge, and spin; some other id e n tify in g properties w ill be given later.
A ccord in g to th eir masses and the dom inant interaction, the fundam ental particles
are grouped into four fam ilies: (a ) massless bosons, (b ) leptons, or lig h t particles,
(c ) mesons, or interm ediate mass particles, and (d ) baryons, or h eavy particles.
(T h e names boson and fe n n io n added to those particles in T a b le 9-1 w ill be ex­
plained in C h ap ter 13, but we m ay state in advance th at ferm ions ob ey the exclu­
sion principle and bosons do n ot.) B aryons and mesons are subject to all four
9.3) Particles and antiparlicles 379

Klectron Muon A0
Ph oton Positron

1900 1910 1920 1930 1910 1950 1900

I
N eu tron
Pion
N e u trin o »

Proton Neutrino,. Resonance

particles

F ig. 9-1. T ime table for the experimental discovery of the fundamental particles. Some
particles were predicted on theoretical grounds prior to their experimental observation,
and others were observed unexpectedly. (Adapted from C. Swartz, The Fundamental
Particles, Addison-WesIey, 1965)

interactions; i.e., strong, electrom agnetic, weak, and gravitation al. Lepton s are
not sensitive to strong interactions, photons are related to the electrom agnetic
interaction, and graviton s to the gravitation al interaction.
One o f the m any puzzling and unsolved questions regarding fundam ental par­
ticles is that the masses o f the particles do not seem to show an y kind o f regularity.
On the other hand, the particles are either uncharged or have charges ± c , a fact
which must he closely related to the law o f conservation o f charge. Sim ilarly, all
ferntions have spin $, except Ω” , which seems to h ave a spin o f f , and all bosons
have zero (m esons) or integral (p h oton ) spin. M o s t o f the particles also have a
m agnetic dipole mom ent.
T h e spin o f the photon is inferred from the fact th at all rad ia tive transitions
in v o lvin g the emission or absorption o f photons by particles, nuclei, atoms, or
m olecules are s trictly forbidden if both in itial and final states have zero total
angular m omentum. T h is shows that the photon carries some intrinsic angular
m om entum , or spin. A more detailed analysis, which we om it, indicates th at the
spin o f the photon is I because the photon is associated with a vector field; i.e.,
the electrom agnetic field. Since the rest mass o f the photon is zero, it can be shown
that the photon spin can be either parallel (m , — + 1 ) or antiparallel (m , = — I),
but never perpendicular (m , = 0 ) to the photon’s m om entum . T h e first case
corresponds to left-handed and the second to right-handed circularly polarized
radiation. T h is result is equ ivalent to the statem ent th at the electrom agnetic field
o f a plane w ave is perpendicular to the direction o f propagation.

ll.it I tU rtivlvx a n d A n iip a r iir lf t t

F o r each particle, there is an associated anliparlicle. T h e antiparticles are listed

in the last column o f T a b le 9-1. A n antiparticle is designated b y the same sym bol
as the particle, but w ith a bar o v e r it. (Som etim es, for sim plicity, the bar is om it­
ted .) A n tip articles h ave the sam e mass and spin as the particles but opposite elec­
trom agnetic properties, such as charge and m agnetic m om ent (oth er properties, to
380 Fundamental particles (,9.3

Particles Antipiirticles

Z0 ZO

vl) vO

A0 A0

C KKW

K»
500

I
I
I
I

_ lL
I
I
y

F ig. 9-2. Particles and antiparticles arranged according to their rest energy and charge.

be m entioned later on, are also opposite). Four particles— the photon, the graviton,
and the ir 0 and η° mesons— are th eir own antiparticles. T h e existence o f an ti­
particles is a requirem ent o f rela tiv ity and quantum mechanics. A n tip articles
were predicted by D irac before they were observed experim entally. In some cases,
the antiparticles have not y e t been identified experim entally, but th eir existence
is assumed theoretically. In Fig. 9 -2 the particles and antiparticles are arranged
in a more sym m etric w ay. T h e first an tiparticle to be observed was the positron.
T h e Am erican physicist C arl Anderson observed it in 1933, when he was an alyzing
cosmic rays w ith a cloud chamber. A n tip roton s were first observed in 1955 b y a
group at the U n ive rs ity o f Californ ia; antineutrons were observed sh ortly afterw ard.
In the case o f the neutrino, there is an im portant prop erty which distinguishes
p article and antiparticle, and which is a consequence o f the fact th at th eir rest
mass is zero (and also because o f p arity noneonservation; see Section 9.6). A
neutrino alw ays has its spin p oin ting in a direction opposite to th at o f its m om en­
tum (which is in the direction o f m otion ), while fo r an antineutrino the m om entum
and the spin are in the same direction (F ig . 9 -3 ). A neutrino is said to have
negative helicity (designated as A ) equal to — I , and an antineutrino is said to
9.3) Particles and Antiparticles 381

have positive helicity, equal to + 1 . T h is p rop erty was found b y means o f an

analysis o f the d ecay of pious and muons and also from /3-decay (see Section 9.4).
For other particles o f spin k which h ave nonzero rest mass (such as electrons), both
particle and antiparticle m ay have either positive or negative helicity, indis­
crim inately; th at is, A = ±1.
PI

F ig . 9-3. The neutrino and anti­

neutrino have opposite helicities. Neutrino, v Antineutrino, 5

N egative helicity Positive helicity

A p article and its antiparticle m ay com bine, disappearing or annihilating each

other. T h e ir total energy, including their rest energy, reappears in the form o f
other particles. In the process several conservation laws must be satisfied. For
example, the electron e ~ and its antiparticle, the positron e + , m ay annihilate,
em ittin g photons, a process called electron p a ir annihilation. I f th eir spins are
opposite and their relative orbital angular m om entum is zero, the process is

e _ + e + -> 27. (9.1)

T h e reason th at tw o photons are em itted is fo r energy and m om entum conserva­

tion. I f the electron and positron are at rest in the lab oratory (which then coin­
cides w ith the C -fram e), the total energy availab le is 2mcc2 = 1.022 M c V and the
total m om entum is zero. I f a photon o f energy Ey = 2mec 2 were em itted, it would
carry a m om entum py = Ey/c = 2mcc and the principle o f conservation o f m o­
mentum w ould be violated , since the initial m om entum is zero. T o conserve energy
and m om entum , tw o equal photons must be em itted in opposite directions. Thus
each photon must have an energy equal to m,,c2 = 0.511 M e V . Photons o f this
energy are observed when positrons from a j3+ -rad ioactive nucleus pass through
matter. A n gu la r m om entum m ust also be conserved and, if the electron and posi­
tron h ave th eir spins in opposite directions, the photons m ust also have their
spins in opposite directions, which requires th at the photons have the same cir­
cular p olarization (o r m ust be polarized in perpendicular directions). W h en either
the electron or the positron (o r b oth ) are not a t rest in the laboratory, the calcu­
lation can be carried ou t using the laws o f conservation o f energy and m om entum
to obtain the energy and m om entum o f the photons as measured in the laboratory.
N o te th at in E q. (9.1) charge is also conserved.
P ro ton -an tiproton annihilation is a m ore com plex process, in v o lvin g the pro­
duction o f several particles, m ost o f them pions. One such annihilation (which
took place in a bubble cham ber) is shown in F ig. 9-4, corresponding to the process

P+ + P — >47Γ+ + 47Γ -J-XTT0. (9.2)

382 Fundamental particles (9.3

Fig. 9-4. Proton-antiproton annihilation. (Photograph courtesy of Brookhaven National

Laboratory)

T h e incom ing antiproton annihilates w ith one o f the protons in the gas o f the
chamber. I f charge is to be conserved, the number o f p ositive and n egative pions
must be the same. T h e number o f 7r°-mesons produced is difficult to ascertain,
since they do not leave any track in the chamber. T h e total number o f particles
produced depends on the energy available.
C onversely, a particle and its an tip article m a y be produced sim ultaneously.
Figu re 9 -5 illustrates the production o f an electron-positron pair b y a photon
entering a cloud cham ber from the le ft; th at is,

7 —» e — -f- e + (9.3)

T h e track o f the photon is not visible. O bviously, fo r an electron pair to be pro­

9.3) Piarticles and anliparlicles 383

duced, the photon m ust have an energy equal to a t least 2mcc 2 = 1.022 M e V .
In order for energy and m om entum to be conserved in E q. (9.3), the process must
occur near a nucleus, which, as a result o f its electrom agnetic coupling w ith the
system, w ill take up the en ergy and m om entum required fo r the conservation o f
both quantities. F o r this reason electron pair production is m ore intense in m ate­
rials which h ave high atom ic numbers (such as lead), since these m aterials provide
a stronger electrom agnetic coupling w ith the elect ron-positron pair. E lectron pair
production is one o f the m ain processes which account for the absorption o f high-
energy photons b y various m aterials. (A t lo w en ergy the photoelectric effect is
the m ore im portant process, and at energies between 0.1 M e V and I M e V it is the
C om pton effect. S c e S e c tio n 1.9 and Fig. 1-19.)
Sim ilarly, a p roton -antiproton pair m ay be produced in a high-energy proton-
proton collision according to the scheme

p + + p + —> p + -F p + + p + -F p ~ . (9.4)

(T h is is not the on ly process that m ay take place in a proton-proton collision.)

Fig. 9-3. Electron-positron pair production. (Photograph courtesy of Brookhaven

National Laboratory)
384 Fundamental particles C9.3

T h is process was used b y the U n iversity o f C aliforn ia group in their experim ents
leading to the discovery o f the an tiproton (see E xam p le 9.2). In order fo r process
(9.4) to occur, the threshold kinetic energy o f the incom ing proton ( if the target
proton is at rest) has to be at least 5.64 G e V (see E xam p le 9.3 for the calculation
o f this valu e).
Our g alaxy seems to be composed m ainly o f particles (rather than a uniform
m ixture o f particles and anti particles) and this makes it stable against annihila­
tion. B u t nothing precludes the possibility th at other galaxies m a y be com posed
prim arily o f antiparticles, although no p ositive eviden ce exists to support this
assumption. In any case it is interesting to speculate on what w ould happen if a
galaxy and an an tigalaxy were to collide. A strophysicists have advanced the idea
th at some o f the explosions observed in distant galaxies m ay be due to a cata­
clysm ic m atter-an tim atter annihilation.

E X A M P L E 9.1. Discussion of positronium, which is a system composed of an electron

and a positron revolving about their center of mass, similar to Ihe electron-proton system
of hydrogen.

S o lu tio n : When a positron and an electron come close to each other, they may form a
stable system whose stationary states are calculated in the same manner as the hydrogen
stationary states discussed in Section 3.2. Recalling Eq. (3.7), we note that, in the case
of positronium, the two particles have the same mass; that is, Wie = M , and therefore
the corresponding Rydberg constant is R ' — %R. When we introduce this value in
Eq. (3.5) with Z = I, the stationary energy levels of positronium are given by

Rh = _ 6 S
1^n no O V*
In 2 n2

The actual energy levels are given by a more complex expression, due to the relativistic
corrections which must be introduced. Because of the possibility of pair annihilation,
according to Eq. (9.1), positronium has a transient life. If the positron-electron pair
moves with zero orbital angular momentum (as in the Is ground state) and their spins
are antiparallel (singlet state 1S), they eventually annihilate into two photons, either
circularly polarized in the same sense or linearly polarized in perpendicular planes, as
previously explained. The half-life of the single state is 1.2 X IO-10 s. I f their spins
are parallel (triplet state, 3S), then conservation of angular momentum as well as certain
additional selection rules related to the symmetry of the system forbid the decay into two
photons. Thus the positron-electron pair annihilate into three photons. The energies of
the photons in each case must add up to 1.022 M e V , which is the total rest energy of the
two annihilating particles. The half-life of the triplet state is 1.4 X IO-7 s. Theexistence
of positronium was confirmed in 1951 by Martin Deutsch. When a beam of positrons
moves through a gas, a certain number of the positrons form positronium atoms before
annihilation. The ratio of probabilities for forming singlet or triplet positronium is I to 3.
Because of the much longer life of triplet positronium, it can enter into chemical reaction
with the atoms or molecules of the gas. In this way positronium halides have been ob­
served. These “ compounds” shorten the life of the positronium because the positron may
annihilate with another electron of the atom or molecule which has opposite spin. Active
research is now being done on the “ chemistry” of positronium.
9.3) Particles and anliparticles 385

E X A M P L E 9.2. The antiproton experiment.

S o lu tio n : Perhaps one of the most interesting experiments in the physics of fundamental
particles is the experiment that led to the discovery of the antiproton. The purpose of
the experiment was to detect particles having a charge — e and a mass mp. Protons, ac­
celerated up to 6.2 GeV by the University of California bevatron, hit a suitable target
which produced several reactions involving K ’s, ir’s, and p ’s, as well as some p~ particles.
A deflecting magnet M i selected only
negative particles, which were allowed to
pass through an opening in the shielding
(Fig. 9-6). The S ’s in Fig. 9-6 are scintilla­
tion detectors and the C’s are Cerenkov
detectors. These instruments are so made
that they are sensitive only to particles in
a certain energy range (see Appendix V I I).
Between S i and S 2 there was placed a
second deflecting magnet M 2, which acted
as a momentum selector, since the radius
of the path was fixed by the position of the
detectors, and only particles with mo­
mentum p = tffir were properly deflected
toward S 2. Because it offered certain
experimental advantages, the magnetic
field was chosen to correspond to a mo­
mentum p = 1.19 GeV/c, which is slightly
less than the momentum at which most
antiprotons should have been produced
(1.75 GeV/c).

F ig. 9-6. Experimental arrangement for

observation of the antiproton.

M any negatively charged particles (K ~ , π - , μ “ ) and a few antiprotons (it was esti­
mated that the proportion was 40,000 other particles to one antiproton) passed through
the magnet M 2 · T o identify the antiprotons, it was necessary to determine the velocity
of the particles. The velocity of an antiproton having a momentum of 1.19 GeV/c is
0.7Sc, while the velocity of a pion of the same momentum is 0.99c. The scintillation
detectors .Si and .S2 were placed 12 m apart; the times required for an antiproton and a
pion with these momenta to go from Si to S 2 were 5.1 X IO- s S and 4.0 X IO-8 s,
respectively. Thus Si and S2 were placed in delayed coincidence, so that they would give
a signal only if S i and S 2 delivered pulses separated by a time interval of 5.1 X 10- s s.
Hence the observation of such delayed coincidences could be considered an indication of
the passage of an antiproton. However, the meson background was so heavy that addi­
tional precautions were required to eliminate accidental coincidences due to the passage
of two different pions through S i and S2 with a delay of 5.1 X IO-8 s. Cerenkov detector
Ci was made sensitive only to particles with velocity greater than 0.80c and C2 was made
sensitive only to particles with velocity between 0.75c and 0.78c. The antiprotons, by the
time they arrived at the Cerenkov detectors, had been slowed down to a velocity of about
386 Fundamental particles (9.4

0.76c. Thus Ci was insensitive to antiprotons Iiut sensitive to mesons, and the reverse
was true for C2. Therefore, to prevent spurious counts, the detector Ci was connected in
anticoincidence and Cs in coincidence with the signals from S i and SV That is, the
experimenters knew that an antiproton had passed through the system only' when (a) S i
and S 2 registered pulses delayed 5.1 X IO-8 s, (b) Ci did not register a pulse, and (c) C2
registered a pulse. As an additional check, the magnetic field of M 2 was varied, and pulses
were received only when the value of the field corresponded to the preselected time of
flight for antiprotons. The experiment— performed by Chamberlain, Segr6, Wiegand, and
Ypsilantis in 1955— was highly successful, and confirmed the existence of the antiproton.

ft .l 1‘ iirtivlv InHtubitity
T h e creation and annihilation processes discussed in the preceding section, as well
as the process o f /9-decay discussed in Section 8.4, are m anifestations o f a more
general p rop erty o f the fundam ental particles: th eir instability. In other words,
given the proper conditions, the fundam ental particles can transform into other particles
as a result o f their interaction. W e shall soon c la rify w hat w e mean when w e say
the proper conditions. P articles which are unstable undergo spontaneous decay,
w ith a w ell-defined half-life. T a b le 9 -2 shows the decay modes and half-lives o f
unstable particles. In cases in which m ore than one decay m ode is possible, the
relative p rob a b ility o f each m ode is also given. In som e decays antincutrinos are
indicated; this is done in accordance w ith a conservation law (th a t o f lepton s)
which will be discussed in Section 9.5. N o te th a t on ly four particles (an d th eir
antiparticles) arc stable against spontaneous d ecay: the photon, the neutrino, the
electron, and the proton. O f all the unstable particles, the one havin g the longest
half-life is the neutron. T h is m ay explain w h y m atter is com posed o f electrons,
protons, and neutrons. N o te th at mesons have a half-life o f the order o f IO - 8 s
(w ith the exception o f the π ° and η °), while the baryon half-lives are o f the order
o f IO- 1 0 S.
One condition necessary for spontaneous d ecay— a con dition im posed by en ergy
conservation— is th at the rest mass o f the parent part i cle be larger than the sum
o f the rest masses o f the daughter particles. In ad dition to energy, m om entum
as well as angular m om entum are supposedly conserved. W e use this assumption
as a guiding principle when we an alyze the decays o f fundam ental particles.
T h e n egative muon was the first unstable particle observed (see F ig. 9 -1 ). It
was discovered in cosmic rays in 1937. T h e decay o f a m uon alw ays results in the
appearance o f an electron. T h ese electrons have a continuous spectrum o f energy,
sim ilar to th at found in /3-decay (F ig . 8 -1 1 ), w ith a m axim um kinetic energy o f
about. 53 M e V . F rom these tw o facts w e deduce th at muon decay cannot be a
tw o-b od y process, and th at at least tw o neutral particles must be produced in
addition to the electron. Since the m axim um energy o f the electron is much larger
than its rest energy (0.5 M e Y '), the m axim um m om entum o f the electron is

Pmux ! —[κιx/r = 53 M eV /c.

T h is m axim um m om entum occurs when the tw o other particles are both em itted
in the opposite direction to that o f the electron, and both particles must carry a
9.4) Particle instability 387

T A B L E 9-2 P article Decay M odes*

It e la t iv e
Pa rticle D e c a y m ode H a lf-life , s
p ro b a b ility , %

P lio ton S ta b le
L epton s

N e u trin o Sta b le
E lectron Sta b le
M uon p - —r e ” + r + V 1.52 X 1 0 - "

Pion TT+ — μ + + e 100

1.80 X I O - 8
—* C+ + V ~10~*

It0 — 7 + 7 99
6 X 10“ 17
-τ 7 + c+ + C- I

Kaon Κ + _ μ+ 4 -ν 63
— T TT+ - I - TTil 21
—►2ir+ + x “ 5.6 8.56 X Ι Ο " 0
- τ ττ°-| -ε+ + y 4.8
—T X 0 + M+ + V 3.4
CO -T JT+ + 2 JT0 1.7
O
/.
O K 0 —τ Tri -f- C+ -f* e 18
S —T IT+ -f- ρ 14
4 X IO "8
—τ TT+ —
{—TT- - f— TT0 6.3
-τ3 χ ° 11.3

K 0 -T T r+ + *- 35
6.0 X Ι Ο " 11
-T 2 *° 15

E ta η° - τ 7 + 7 33
-T TT0 + 7 + 7 20
—τ 3ττ° 20 C l O " 10
—τ χ + + χ ~ + χ ° 22
-Τ Χ + + Χ - + 7 5

P roto n S table

N e u tro n η 0 —τ ρ + + e- + V 7.0 X IO 2

Lam bda Λ ° —τ ρ + + χ - 66
1.76 X 1 0 - * °
Uu + X0 34

S igm a Σ + — P+ + X 0 53
5.6 X Ι Ο ' 11
to - T Il0 + X + 47

5 2° - Λ° + 7 < 7 X Ι Ο " 15

2 - — η0 + χ- 1.1 X I O " 10

Xi E0 -* Λ ° + χ° 2.0 X I O - 10

Η- -τ Λ0 + χ - 1.2 X Ι Ο " 10

O m ega S2- — Λ ° + K - 50 1 0 -1 0

-> E 0 + χ - 50

* T o obtain the decay of antiparticles, change all particles into antiparticles on both
sides of the equations.
388 Fundamental particles (9/4

F ig. 9-7. Decay of a π - meson followed by the decay of the muon. (Photograph courtesy
Brookhaven National Laboratory)

to ta l m om entum o f 5 3 M e V / c . I f the particles are neutrinos, th eir total energy

is then 53 M e V . Thus the total energy released in muon decay is about IOG M e V 1
which is practically the rest energy o f the muon (T a b le 9 -1 ). T h e spin o f the
muon has been measured independently and found to be 0-; thus the law o f conser­
vation o f angular m om entum is another factor th at would forbid the decay o f a
muon into an electron and a neutrino, each havin g spin £. H o w ever, this law does
allow for a muon decaying into an electron and tw o neutrinos. T h erefo re we m ay
sa fely assume th at the decay of a n egative muon can be represented b y the decay
m ode given in T a b le 9-2.
T h e next partiqle to be observed was the pion. I t was first discovered in 194G in
special photographic emulsions (see Ap p en d ix V I I ) exposed to cosmic rays, and
shortly afterw ard artificially produced (b y protons accelerated in the synchrotron
at B erk eley). T h e existence o f this particle had been predicted in 1935 b y the
Japanese physicist H id eki Y u k a w a to explain the short range o f nuclear forces
(see Section 9.8). T h e muons resulting from pion decay consistently h a ve a fixed
kinetic energy o f about 4.1 M e V , which indicates th at pion decay is a tw o-b od y
problem . T h erefo re w e m ay assume that in pion decay, in addition to the muon,
g/ι) Particle instability 389

a neutrino is e m itted in the opposite direction. Since the m om entum o f a muon

w ith the ab o v e kinetic energy is 29.5 M eV / c, this m ust also be the mom entum o f
the neutrino. T h e neutrino energy is then 29.5 M e V . Thus the total energy re­
leased in pion decay is 105.7 M e V + 4.1 M e V + 29.5 M e V = 139.3 M e V , which
again app roxim ately agrees w ith the rest energy o f the pion, 140 M e V . W e may
thus assume th at the decay scheme o f the pion is as indicated in T a b le 9-2. From
the decay π + —» μ + + v, w e conclude th at the spin o f the pion is either 0 or I.
From an analysis o f other processes in v o lvin g pions, w e conclude that the spin
is 0: F igu re 9-7 shows the decay (in a bubble cham ber) o f a pion into a muon,
follow ed by the subsequent decay o f the muon into an electron. T h e accom pany­
ing neutrinos do not leave an y track. O bservation o f these double events is very
common.
Sim ilarly, Fig. 9-8 shows the d eca y o f a kaon into three pions in a photographic
emulsion. An alysis o f the m om enta o f the three pions shows th at no further neu­
tral particles are em itted in the process; this is consistent with the laws o f conser­
vation o f m om entum and energy. On the other hand, F ig. 9 -9 shows the decay o f

1 5-M cV «--meson 17-M eV «-m eson leaves

V em ulsion strip a t Λ

K-m eson

I
43-M c V x-m eson

F ig. 9-8. K-meson decay into three pions (the τ -mode). (Fhotograi+ courtesy of
Brookhaven National Laboratory)
390 Fundamental particles (I9.4

f U A
Ir Ί! i
' I: U ~ ’’
' i
I! ■
* I1 i r {
i'
'«I II
H if
* r

tl\ I
I
I

i iti
i
\ I [■
r I .
\

Π; I r i
i f ’I I- H:
,
*
- ;· I ! '
HM H
: I .il·
I r '
- I
!I

Si B iI
Ii I Ϊ i .,;
!; I I I' ■

IX ■

F ig. 9-9. K-meson decay into two pions (the 0-modc). (Photograph courtesy of Brook-
haven National Laboratory)

a kaon into a charged and a neutral pion. F igu re 9 -10 shows a m ore com plex
process, in which there is an initial prolon -an tip roton annihilation, g ivin g rise to
a series o f particles which undergo subsequent decays. T h e whole process can be
expressed by

Each o f the processes has been carefully checked b y means o f the laws o f conserva­
tion o f energy and m omentum. Such a check enables us to id en tify the neutral
particles which do not leave an y track.
T h e instability o f a given particle is also d isplayed b y the fact that, in a high-
energy collision between tw o particles, several new particles m ay be produced.
9A) Particle instability 391

F ig. 9-10. Events triggered by a proton-antiproton annihilation. (Photograph courtesy

of Brookliaven National Laboratory)

F o r exam ple, in a proton-proton collision, the follo w in g processes m ay occur:

.P + + P +
(9.6)
N 1
p T - f n + Tr

N o te th a t in each case a pion is produced. T h e proton-proton collision is the proc­

ess b y which pions are produced profusely in th e laboratory. I f one o f the pro­
tons is a t rest in the lab oratory, the threshold o f energy o f the other proton is
392 Fundamental particles

F ig. 9-11. Events triggered by a K ~-p collision. (Photograph courtesy of Brookhaven

National Laboratory)

about 300 M e V (see E xam ple 9.3). A t higher energies, other particles, such as a
p roton -antiproton pair, m ay result.
Figu re 9-11 illustrates a m ore com plex process b y which a K - and a p + collide,
resulting in several particles which suffer subsequent decay. T h e w hole observed
process can be described by

K - + pH Η " + Iv 0 +
7T+ -f (9.7)
0
+ Λ
L-> 7Γ + p +

Thus a t high energy the collisions between particles are not elastic. T h e particles
 Particle instability 393

Fig. 9-12. Events triggered by a cosmie-ray proton colliding with a proton in the
atmosphere.

can no longer be considered as billiard balls, w hich is a useful approxim ation at

low energies.
M a n y o f the processes in v o lvin g fundam ental particles have been observed in
cosmic rays', th a t is, the flux o f particles (m ostly protons) falling on the earth as a
result o f nuclear processes occurring in the sun and other parts o f the universe.
C osm ic-ray particles trigger a chain o f reactions when th ey in teract w ith nuclei
in the upper atm osphere. One such reaction is shown in Fig. 9-12. Such a process
continues until the energy is no longer great enough to produce new particles, and
on ly stable particles rem ain.

E X A M P L E 9.3. Calculation of the threshold energy for a process in which a projectile

collides with a target at rest in the laboratory, resulting in several new particles.
394 Fundamental particles (9.4

S o lu tio n : Designating the projectile and the target by P i and P 2 and the resulting
particles by P,, we may · iitc

P i + P 2 -> Σ , P.-

lf the momentum of P i is p, in the L-framc, its total energy is c V wife2 -j- p~. Since Pa
is at rest in the Λ-frame, its total energy is m2c2. Thus the total energy in the /.-frame is

E = cV ^ntic2+ p2 + m2C2

and the total momentum is p. In the C-frame of reference the momentum of the two
particles is zero; that is, p ' = 0 (see Appendix Ij. W e designate the total energy of the
system in the C-Frame by E '. Because of the energy-momentum relation, the quantity
E 2 — C2P2 is invariant under a Lorentz transformation relating two inertial frames of
reference. Therefore, keeping in mind that />' = 0, we have

E2 - C2 P 2 = E '2.

The laws of conservation of energy and momentum require that, after the process has
taken place, the total energy of the products in the C-frame still be E ' and the total mo­
mentum be zero. Obviously the minimum energy required for the process corresponds to
the situation in which all the resulting particles are at rest in the C-frame, so that the
total energy in such a frame is E ' = Σ ·* 71»®2· Substituting values in the preceding equa­
tion, we get
2 I , 2 4 , „ Sa / 2 2 . 2 -V-. .2 4
true + WI2C -J- 2moc V mic + p = (z.,w i,) c.
But if Et is the kinetic energy of the projectile in the /.-frame, then

V mic2 2 T1 P2 - „ ,
Ek + « lie ■
2

M aking this substitution in the preceding equation and canceling the common c2 factor,
we get
(mi + tno)2c2 + 2m2Ek = ( Σ .Ηί.)2ε2.
Thus
E t = — QM/2m2, (9.8)

where Q = (»u -J- m2 — Σ>η + and M = mi + » 12+ Σ ’" · · Equation (9.8)gives the
threshold kinetic energy which the projectile must have for a given process to occur. If Q
is positive, 110 threshold kinetic energy exists and the rest energy of the initial particles is
enough to produce the final particles. Only if Q is negative does a threshold energy exist.
W e shall illustrate the use of Eq. (9.8) by applying it to two special cases.
a) Threshold for pion production in proton-proton collision. Considering a neutral pion,
wc have that p + -J- p + —» p + - f p + + ir0. Therefore

Q = — m,c2, .1/ = 4 Wil, + m,, and m 2 = mp,

resulting in
_ m,r2(4mi d l i O = / m A ^ 29()
2 Wp \ 2 Wp/

For a charged pion, a similar result is obtained.

9A) Particle instability 395

b) Threshold fo r antiproton production in proton-proton collision. The process is now

p + -j- p + —* p + + p + + p + -f- P~- AU particles have the same mass mp. Then

in 2 = nip, Q = — 2nipc2, and .1/ = Gm1,,

giving, for the threshold energy,

E t = (2mpC2) (Gmp) /2m„ = 6mpc2 = 5.G4 X IO3 M eV = 5.64 GeV.

E X A M P L E 9.4. Determination of the magnetic moment of the A 0-Iiyperon.

S o lu tio n : W e shall now describe an interesting experiment which illustrates the tech-
nicpies used to determine the properties of fundamental particles. W e refer to the mea­
surement of the magnetic moment of the A°-hyperon. The method, which is similar to
that used to determine the magnetic moment of any hyperon, involves three steps: (a)
producing a polarized beam of A 0, (b) causing the polarized beam to pass through a
strong magnetic field which produces a change in the direction of the magnetic moment,
(c) measuring the angle of rotation of the magnetic moment.

P o ly eth y len e ta rget

Emulsion stack

A v e r a g e direction o f
S a t produ ction in
A®-cm fram e

Average direction of S
at decay if aλ < G
(also average direction of
emission of decay pion
in the A0-CM frame)

F ig. 9-13. Schematic diagram of the A°-magnetic moment experiment.

There have been several experiments designed to analyze the decay of polarized A ° ’s
in a magnetic field. W e shall describe the one performed at C E R N (European Organiza­
tion for Nuclear Research) in 1964. A beam of negative pions from the C E R N proton
synchrotron, having a momentum of 1.05 GeV/c, falls on a polyethylene target (Fig. 9-13),
where the reaction ir~ -E p + —> A 0 + K 0 takes place. The momentum is chosen to cor­
respond to the energy at which the cross section for the reaction is maximum. Since the
energy of the ir~ particle is close to the threshold energy, 0.78 GcV' (see Eq. 9.8), the
A 0 and K 0 are produced, relative to the laboratory, mainly in the forward direction
because they are practically at rest in the C-framc of the process.
T he A 0 are strongly polarized with their spin S normal to the plane of production
(that is, the plane determined by the directions of motion of the incident tt~ and the
resultant A 0). The A 0 produced at angles between 13° and 23° with respect to the direc­
tion of incidence are made to pass through a strong magnetic field of 15 T , perpendicular
to both pa and S.
396 Fundamental particles

According to Eq. (7.5), the magnetic moment of the A 0 should be written as

Λ/λ = g*(e/2mA)S,

where g.\ is the gyromagnetic ratio of the A 0. It is customary, however, to write the mag­
netic moment in the form

Mh = g h (m p/ m h )(e / 2 m „ )S = p h (e / m p) S ,

and the quantity sought experimentally is μ,\ = bg\(jnp/mλ), which gives the A 0 mag­
netic moment in nuclear magnetons. In the presence of a magnetic field ffi there is a
torque r = .VfA X ffi, so that the equation of motion of the spin is dS/dt = T or

dS
— = p.\(e/mp)S X f fi = —μΑ(β/ηιρ)(Β X S,

and S precesses around ffi with an angular velocity*

Ω = — p.\(e/m p)<&.

If μ\ is negative, S will process around ffi in the sense shown by the arrow marked A in
Fig. 9-13 and in the opposite sense if μΑ is positive. A fter a time I the spin S has rotated
an angle Θ = Sit. I f v is the velocity of the A 0 and I the distance moved through the
magnetic field, we have I = l/v, and thus

e = P h (— ) — · (9.9)
\ mp/ »

Thus if one can observe Θ, one can determine μΑ in terms of known quantities.
Actually the most interesting (and difficult) part of the experiment is the measurement
of 0, which requires determining the direction of S after the Ah traverses the magnetic field.
One can measure the angle 0 by observing the angular distribution of the products of the
A°-decay. A stack of photographic emulsions are placed in the direction of the A°-beam,
as shown in the figure. Many A°'s decay in the emulsions, according to the process
A 0 —* 7Γ- + p + . Both decay products, since they are charged, leave tracks in the emulsions.
In the decay A 0 —* ir~ -f- p +, the pions arc distributed anisotropicallv (but symmetri­
cally) relative to the direction of S in the C-frame of reference of the A 0. Given that φ
is the angle between the momentum of the π ~ and S, the angular distribution of the ir~ in
the A 0 C-frame is found experimentally to be proportional to I + k cos φ, corresponding to
a strong maximum in the direction of S. Hence, by analyzing the angular distribution of
decay pions in a beam of polarized A ° ’s, one can determine the direction of polarization of
the A 01 which is the direction of S, and in this way obtain the angle Θ. Then, applying
Eq. (9.9), one can find μ.ν· The actual calculations require a careful consideration of quan­
tities referred to the laboratory and to the A°-center-of-mass frames. The value obtained
at C E R N was μΑ = — 0.5 ± 0.28 nuclear magnetons. T h e value predicted theoretically

* Because of the energies involved, we must perform the calculation by means of rela­
tivistic mechanics. For simplification, however, we use a nonrelativistic calculation which
gives the correct result (insofar as the value of 9. is concerned) when the A 0 moves per­
pendicular to ffi.
9.5) The conservation laws 397

on the basis of the Gell-Mann “eightfold-way” theory (Section 9.8) is —0.95 nuclear
magnetons. The magnetic moment of the A 0 had been previously measured at Brook-
haven, Argonne, and the University of California, using somewhat similar methods. The
results were, respectively, — 1.5 ± 0.5 nm, 0 ± 0.6 lira, and — 1.39 ± 0.7 nm. The
most recent measurement (I960) by H ill and his collaborators at the Brookhaven National
Laboratory is — 0.73 ± 0.16 nm.

9 .5 T h e I 'ems»‘r rat ion L a irs

In all the processes illustrated in the previous section, it has been found th at the
follo w in g conservation laws hold w ith ou t exception:

(1 ) C onservation o f m om entum
(2 ) C onservation o f angular m om entum
(3 ) C onservation o f energy
(4 ) C onservation o f charge

W ith in the lim itation s imposed b y these four conservation laws, at first sight
the fundam ental particles appear as a wild group o f physical entities tending to
transform into one another w ith ou t any apparent order in these processes. W e
m ay understand, for exam ple, th at the electron and the positron are stable because
there are no other lighter charged particles into which they m igh t decay w ith ou t
viola tin g charge conservation. Hut w hy is the proton stable and w hy does it not
decay, for exam ple, according to the scheme p + —* T + + u? W h y is it th a t cer­
tain processes— such as 7 —> e ~ - f p + , A 0 —* p _ + i r + , or π + + P + - * 2 + -(- i r + ,
which com ply w ith the ab ove conservation law s— do not occur in nature? W h y
do the particles have such an app aren tly random mass spectrum ?
T h e situation is sim ilar to th at o f an alchemist in the M id d le A g es tryin g to
understand chem ical reactions w ithout know ing atom ic or m olecular structure.
Physicists to d a y are a c tiv e ly struggling to find some order in this apparent chaos.
F ortu n a tely, a certain degree o f order has been brought abou t b y the discovery
o f new conservation laws which resemble the law o f conservation o f charge rather
than the first th ree conservation laws. These laws are:

(5 ) C onservation o f leptons
(6 ) C onservation o f baryons
(7 ) C onservation o f isotopic spin
(8 ) C onservation o f strangeness

W e shall now briefly discuss each o f these laws in turn.

E xp erim en tal data lead to the conclusion th a t mesons and photons (and in gen­
eral all particles o f spin 0 or I ) can be produced or annihilated in an y number (this
is one o f the reasons for calling them bosons). On the other hand, leptons and
baryons are restricted w ith regard to the num ber which m ay be produced or
annihilated in a single process. F o r exam ple, the process o f electron pair production
Ύ —* e ~ -f- e + , in which tw o leptons— an electron and its antiparticle, a positron—
398 Fundamental particles (9.5

are created ou t o f a photon is possible. B u t the process o f electron-proton produc­

tion 7 —> e ~ + p + , which could com ply with th e first four conservation laws, does
not occur. I n this process (which is not observed ) on ly one lepton and one baryon
are produced. I t is experim ental facts o f this kind w hich form the basis for the
fifth and sixth conservation laws.

C o n s e r v a tio n o f le p to n s . L e t us introduce a lepton quantum number £ de­

fined such th at £ = + 1 fo r lepton particles and £ = — I for lepton antiparticles.
N on -Iep ton particles have zero lepton number. T h en

in any process, the total lepton number must remain unchanged.

Considering som e examples, we have that, in the process 7 —» e — + e + , the lep­

ton number on the left is £ = O and on the righ t £ = +1 — 1 = 0. H ow ever, in
the nonobserved process 7 —> e — + p + , w e have £ = O on the left and £ = + 1 on
the right, so th a t the conservation o f IeiDtons is violated . T h e law o f conservation
o f leptons requires th at E q. (8.14) be w ritten in the form

n —> p + + e — + v
£ = O O + 1 - 1 (9.10)

to assure a to ta l lepton number o f zero on both sides. T h u s conservation o f lep­

tons requires that, in jS~-decay, an antineutrino v and not a neutrino be em itted.
W e must also w rite E q. (8.17) in the form p + + v —» n + e + , with a total lepton
number £ = — I on both sides. T h is is w hy, in the C ow an-R cines experim ent
(E xam p le 8.6), it was an antineutrino which was detected. N o te th at Eqs. (8.1.5)
anil (8.16) fo r β + -deca y and electron capture require a neutrino to ob ey lepton
conservation. B y exam ining the decay schemes o f T a b le 9-2, the student should
v e rify the law o f conservation o f leptons in each case and ju stify the fact th at an
antineutrino is indicated in som e cases.
L e t us m ention in passing the fact th at recent (1962) experim ental eviden ce
seems to suggest th at the neutrinos resulting from pion d ecay are not identical to
those produced in muon decay or in /8-decay. T h e experim ent perform ed by a group
from C olu m b ia U n ive rs ity w ork in g w ith B rook h aven L a b o ra to ry ’s A lte rn a tin g
G radien t A ccelerato r is shown schem atically in F ig. 9-14. A h ea vily shielded
spark cham ber was exposed to th e anti neutrinos resulting from pion decays accord­
ing to π + —» μ + + V. T h e pions had been produced b y high-energy protons striking
a convenient target. T h e antineutrinos colliding w ith the nuclei in the spark cham ­
ber, if they w ere identical to those produced in + d e c a y , could produce cither one of
the reactions p + + P —* n + e + or p + + v —* η + μ + . H ow ever, if there were tw o
kinds o f neutrinos, on ly the second reaction should be allowed. A fte r a run o f
several days, in which an estim ated IO 14 antineutrinos passed through the spark
cham ber, abou t .50 processes were observed in which muons were produced; but no
positrons were observed. T h is suggests th a t the first reaction is forbidden, and th at
the neutrinos produced in pion decay are not the same as those produced in + d e c a y .
9.5) The conservation laws 399

Steel
shielding

T h erefore it is now usual to write

π yμ + ν μ, » μ 4 + Ρμ,
μ~ e -f- ν μ + Pei ■ e + + Ρμ + P»,
η ■ P+ + e + P,ej η + e+ + Vc,

P + + Pe Il P + + Pil η μπ

where νμ designates the neutrino associated w ith the muon in pion decay and vc
the neutrino associated w ith the electron in muon or nucleon decay.

C o n s e r v a tio n o j b a r y o n s . D efin in g a baryon quantum number b such th at

b = + 1 for all baryon particles, b = — I for all baryon antiparticles, and zero for
all non-baryon particles, we m ay say th at

in any process, the total baryon number must remain unchanged.

T h e student m a y v e rify th at this la w is satisfied in all processes previou sly m en­

tioned in v o lvin g baryons, such as Eqs. (9.2), (9.4), (9.5), (9.6), and (9.7), as well
as in the decay schemes o f T a b le 9-2. Since the proton is the lightest o f all b ary­
ons, its decay into lighter particles (which cannot be baryons) would v io la te the
law o f conservation o f baryons, and this explains w h y the proton is a stable par­
ticle. T h u s the w orld in which w e liv e is, to a certain extent, the result o f the
laws o f conservation o f leptons and baryons.

C o n s e r v a tio n o f is o t o p ic s p in . In F ig. 9-2, the particles and antiparticles

were grouped according to th eir masses or rest energies. W h en w e consider on ly
those particles affected by strong interactions (m esons and baryons), we note th at
they occur as m u ltip lets; th at is, singlets (j/°, Ω- , Λ 0), doublets ( K + and K 0, p +
and η 0, Ξ 0 and H ~ ), and triplets ( 2 + , 2 °, and S - , 7r+ , 7t°, and i r ~ )* . T liis suggests
that we m ay q u a lify each m u ltip let by a new qu an tity, called isotopic spin τ , such
that 2 r - f I gives the number o f particles in each m ultiplet. Thus T = 0, £, I, . . .

* The π0, being identical to its antiparticle, has been placed in the center of the diagram
and the set π +, τ ° , ir_ must be considered in a special way.
UOO Fundamental particles C9.5

T A B L E 9-3 Isotopic S pin (r , T z) , S trangeness ( i), an d

IIy pereh arge (y ) o f .Mesons an d B aryo n s*

Particles T Tz a V

Mesons
jr+ , τ 0, π ~ I (1 ,0 ,-1 ) 0 0
1
K +, K 0 2 ( £. - £ ) I I
V0 O 0 C 0

Baryons
P +i 11 £ (£ . — £ ) 0 I
A0 0 0 — I 0
2 + Σ~~ I ( I , 0, - I ) - I 0
E0 E - £ (£, — £) -2 —I
0- 0 0 -3 —2

* The strangeness and hypercharge of antiparticles have signs

opposite to those of the corresponding particles. Mesons and
baryons are frequently designated by the common name of hadrons.

fo r .singlets, doublets, triplets, and so on. W e use the w ord “ isoto p ic” because τ
refers to particles which have practically the same mass and spin and thus occupy
the same place on a mass scale.* W e m ay note th at τ bears some resem blance to
an angular m om entum J , which m ay h a ve 27 + 1 orientations in space, each
characterized by a value o f its Z-com ponent J z, and this is w hy the name "s p in ”
was given to r . T h u s w e m ay consider the isotopic spin as a ve cto r in a certain
representative space called isotopic spin space. T h e ve cto r has a length γ + ( τ + I)
and it has 2 t + I possible orientations rela tive to the Z-axis, corresponding to the
possible values o f its Z-com ponent given b y τ . = ± r , ± ( t — I ) , ± ( r — 2 ), . . . .
Each particle in a m ultiplct corresponds to a value o f t z, w ith values assigned
in order o f decreasing charge. F o r exam ple, we h ave Tz = + £ fo r protons and
Tz = — \ for neutrons. P article and an tiparticle m ultiplets have the same iso­
topic spin r , but opposite values o f t z. T h e isotopic spin o f mesons and baryons
is given in T a b le 9-3.
T h e total isotopic spin T o f a system o f particles is obtained by adding, in v ec­
to r form, the isotopic spins o f each particle, using the same addition rules as for
angular m om entum (Section 3.8). Consider, for exam ple, the system p + + p + .
T h e tw o particles have τ = £ each, which m ay add to g iv e a resultant isotopic
spin T = I or 0. B u t T z = £ + £ = I. T h u s a system o f tw o protons neces­
sarily corresponds to T = I. B ut the system p + + n has T , = £ — £ = O and
thus the total isotopic spin m ay be T = I or 0. Sim ilarly π + + p + m ay h ave a
total isotopic spin o f § or £. B u t T z = I + £ = §, so th at T = necessarily.
On the other hand, π ° + p + and π - + p+ , havin g T z = £ and — £, resp ectively,
m ay correspond to either T = \ or £.

* The names isobaric spin and isospin are also used to describe this property.
9.5) The conservation laws 501

I t seems th at the strong or nuclear

interaction is charge independent. For
example, there is am ple experim ental e v i­
dence th at the nuclear interaction for the
pairs p + p + ( T 2 = + 1 ), n p + ( T 2 = 0),
and n n ( T 2 = — I ) is the same. T h ere­
fore the strong interaction is independent
of the total value o f T 2 for the interacting
particles. Thus the strong interaction
between two particles depends only on their
total isotopic spin T.
>r-energy, M e V
F or example, in the scattering process
F ig. 9-15. Cross section for (a) ir+ + p +
7T+ -)- P + —» 7T+ + p+, and (b) π - + p + collisions as a function
of energy.
we have T 2 = §, necessarily correspond­
ing to T = § on both sides o f the equation, and the observed cross section
varies w ith the energy o f the 7r+ -projectile, as shown in Fig. 9-15, curve (a ),
w ith a pronounced maxim um at an energy close to 300 M e V . H ow ever, in the
case o f

tr- + P + (scattering),

7r + p+

7Γ° + n (reaction ),

we have T 2 = — J, which m ay correspond to either T = § or T h e total ob ­

served cross section is shown in curve (b ) o f F ig. 9-15. T h e peak corresponding
to T = § falls a t pra ctica lly the same en ergy as in the previous case o f ir + -f- p +
for the same total isotopic spin, but at about 1000 M e V a second peak is observed
which is attribu ted to the T = £ state.
A s a result o f the analysis o f processes in which strongly interacting particles
participate, we m ay state that

the total isotopic spin T is conserved in strong interactions.

T h e conservation o f total isotopic spin is a rigorous law on ly for strong inter­

actions but it can be violated in electrom agnetic or w eak interaction processes.
F o r exam ple, in the observed process K 0 —> π + + π ~ , w e have T = ^ on the le ft
and either T = I or 0 on the right, so th at T is not conserved.
In ad dition to the conservation law o f total isotopic spin, we have that

both the strong and electromagnetic interactions conserve the total T 2

component o/ the isotopic spin.

T h is is a rigorous law, follow ed in all cases, and is fu lly equ ivalent to the law o f
conservation o f charge.
h0'2 Fundamental particles {9.5

C o n s e r v a tio n o f s tra n g e n e s s . A n oth er a ttrib u te invented to characterize

particles subject to strong interactions is the strangeness λ , defined so th a t the
charge o f a p article in a m ultiplet is g ive n by

q = β (τ , + J t -F (9 .1 1 )

T h e values o f j. are given in T a b le 9-3. P articles and antiparticles have opposite

strangeness. T h e law o f conservation o f strangeness requires that

the total strangeness S must remain the same in processes due to strong
or electromagnetic interactions.

F o r exam ple, the process v ~ -F p + —* n 0 + A 01 which com plies w ith all the other
conservation laws, is not observed because the to ta l strangeness on the le ft is zero,
w h ile on the righ t it is — I. H ow ever, processes such as π * + P + —* - + + K + and
7r“ -F p + —> A0 -F K 0 do occur. In both cases the to ta l strangeness remains equal
to zero. T h a t is, in all pion-nucleon collisions (a system havin g zero strangeness),
hyperons must be produced in pairs w ith equal but opposite strangeness, a phe­
nomenon called associated production. A c tu a lly it was the consistent observation
o f the associated production o f certain hyperons which provided the clue to the
law o f conservation o f strangeness.
T h e conservation o f strangeness is not a rigorous law ; it can be v io la ted by weak
interactions which allow a change o f strangeness o f ± 1 . In m ost baryon decays
(T a b le 9 -2 ), the conservation o f strangeness is violated , indicating th at the decays
take place by means o f weak interactions. F o r exam ple,

Η- -* A0 -F ir ~ (AS = + 1),
U 7T- - I - P + (A S = -I ).

H yperon s cannot decay into baryons through the strong interaction w ith conser­
v atio n o f strangeness, because the Q o f such processes is negative. T h is explains
w h y the hyperons decay so slow ly (ab ou t IO-10 s) com pared w ith the tim e in­
v o lv e d in th eir production or annihilation in collisions b y means o f strong inter­
actions, which is about IO -23 s. From these tw o tim es w e m ay conclude th at the
strength o f the weak interaction is about IO-13 o f the strength o f the strong
interaction.
W e might m ention at this point that another param eter which m ay be used to
classify particles instead o f strangeness is the hypercharge, defined as y = 6 -F A.
Values o f the hypercharge arc given in T a b le 9-3. T h e law o f conservation o f
strangeness can be replaced b y a law o f conservation o f hypercharge, due to the
law o f conservation o f baryons and the definition o f y.

T h e new conservation laws which we h ave introduced in this section m ay seem

m ore or less ad hoc conventions to explain the experim ental facts. H o w ever, the
fact th at th ey are consistently applicable to a large number o f situations suggests
th at they h ave a deeper physical m eaning. A t present th eir connection w ith the
physical properties o f particles is not w ell known in all cases, and is a subject still
open to further research.
9.6) Invariance, symmetry, and conservation laws h03

9.0 In v a r ia n c e , Sym m etry, a n d Contterraiion Lairtt

Some o f the conservation laws we h a ve just discussed can be traced Ixick to certain
invariance and sym m etry properties o f physical system s which we shall now
briefly consider.

S p tic e t r a n s la t io n . L e t us assume that space is homogeneous and uniform ;

i.e., it has translational sym m etry a t all points. W e must conclude then th at a
ph3'sical system w ill behave the same no m atter w here it is located in an other­
wise e m p ty space. Using a more m athem atical term inology, the description o f
the properties o f an isolated physical system is invariant w ith respect to a trans­
lation o f the system relative to a fram e o f reference. F o r exam ple, an isolated
molecule, com posed o f several electrons and nuclei, must be described in exactly
identical term s no m atter where it is located rela tive to an observer. On the other
hand, we know that the total m om entum o f an isolated system is constant. Thus
it can be shown that

the conservation o f momentum o f an isolated system is a result o f trans­

lational invariance o f the laws describing the system.

In some cases the system m ay not be isolated, but the physical environm ent
m ay exh ibit certain translational sym m etry. C onsider an electron placed between
tw o infinite parallel planes carryin g equal opposite charges. O bviously the physical
conditions do not change if the electron is displaced parallel to the planes. We
know then th at when the electron is set in m otion, its mom entum parallel to the
planes is constant. (T h is is usually stated b y saying th at the electric field pro­
duced b y the charged planes is perpendicular to the planes.) T h u s we again find
that the conservation o f momentum in a given direction is a consequence o f transla­
tional invariance o f the physical conditions in that direction.

S p a c e r o t a t io n . I f we assume th at space is isotropic (i.e., that it has rota­

tional sym m etry at any p oin t), then the description o f the properties o f an iso­
lated system m ust be independent o f its orientation in space relative to a given
fram e o f reference. L e t us again consider an isolated m olecule: the description o f
its properties is independent o f the orientation o f the m olecule relative to the ob­
server. On the other hand, we know th at the total angular m om entum o f an iso­
lated system is constant. I t can thus be shown that

the conservation o f angular momentum o f an isolated system is a result

o f rotational invariance o f the laws describing the system.

In som e cases, even though a system m ay n ot be isolated, the physical system

m ay exhibit a certain rotational sym m etry. F o r exam ple, a central field o f force
has spherical sym m etry. W e then know that, as a result o f the sym m etry, the
angular m om entum (re la tiv e to the center o f force) o f a particle m ovin g under
central forces is constant. I f the field has cylin drical sym m etry, as in the case o f
the force on an electron in a d iatom ic m olecule or a charged particle in a uniform
m agnetic field, then the com ponent o f th e angular m om entum rela tive to the sym ­
UOU Fundamental particles (1
9.6

m etry axis remains constant. T h u s we again find th at the conservation o f angular

m omentum about a given direction is a consequence o f rotational symmetry o f the
physical conditions relative to that direction.
B oth translational and rotational sym m etry impose certain lim itations on the
m athem atical form o f physical law s; how ever, this is a subject that we cannot
explore any further here.

T i m e t r a n s la t io n . In variance w ith respect to tim e translation means that

if we prepare a physical system and leave it to e v o lv e w ith out external interfer­
ence, the evolution o f the system w ill be the same irrespective o f the tim e a t which
it was prepared, or in other words, o f the chosen origin o f time. Using a som ewhat
m ore elaborate logic, we can show th at

the conservation o f energy o f an isolated system is a consequence o f the

invariance o f the Iaxvs describing the system relative to the chosen o rig in
o f tim e;

th at is, rela tive to a translation o f tim e. T h e laws o f both classical and quantum
mechanics are in varian t relative to tim e translation.

G a u g e t r a n s f o r m a t io n . Our fourth conservation law, th a t o f charge, is a

little m ore difficult to associate, in an elem entary w ay, w ith a sym m etry trans­
form ation and an invarian t property. W e can show that

charge conservation is a result o f the invariance o f the laics o f the elec­

tromagnetic field (i.e., M a xw ell’s equations) with respect to a “gauge”
transformation.

W e cannot fu lly explain in this te x t w hat is meant b y a gauge tran sform ation *;
a sim ple case o f a gauge transform ation is a change in the zero o f the electric (o r
scalar) potential, a change which does not affect the electric field or the form o f
M a x w e ll’s equations. A n oth er ty p e o f gauge transform ation is a change o f phase
o f the w ave function; i.e., the replacem ent o f ψ by e'fy . T h is obviou sly leaves the
p rob ab ility density |ψ|2, which is the observable quantity, unchanged.

I s o t o p ic s p in r o t a t io n . A r e there other sym m etry operations th at can be

related to conservation laws? W e have indicated th at the isotopic spin is conserved
because o f the charge independence o f the strong interaction. W e can put this
in the same form as the fou r preceding conservation laws b y saying th at

the isotopic spin is consen'ed because strong interactions are invariant

with respect to rotations in isotopic spin space.

* See, for example, Panofsky and Phillips, Classical Electricity and Magnetism, second
edition, Reading, Mass.: Addison-Wesley, 1962, Section 14-1.
9.6) Invariance, symmetry, and conservation laws 405

T h is invariance means that the interaction must contain the isotopic spins T 1 and
T2 o f the interactin g particles on ly in forms such as T 1 · r 2l which is rotation a lly
invariant, but n ot as T11Tz2, which is not. U n fortu nately, we cannot elaborate
more on the m athem atical m eaning o f the ab ove statem ent, but its sim ilarity to
the conservation o f angular m om entum under central forces is obvious.

C h a rg e r e f le c t io n . Eleclrom agnelic and strong interactions rem ain invariant

i f all charges are replaced by those with opposite sign (th a t is, q —> — 9), an operation
which is called charge reflection. One can show th at this leads to the conservation
o f the Z -com ponent T z o f the total isotopic spin in those interactions.

N o sim ple sym m etry p rop erty or invarian t b ehavior has y e t been associated
w ith the conservation o f leptons and baryons. T h e re are, however, three m ore
sym m etry operations o f great im portance in the fundam ental behavior o f m atter.
T h e y are: p arity P , charge conjugation C, and tim e reversal T .

M irro r M irro r

(a) (l>)
F ig. 9-16. Reflection in a plane of (a) momentum, (b) angular momentum.

P a r it y . T h is concept, which w e considered before in Section 2.9, refers to

the operation o f space reflection, either in a plane or through a point, such as the
origin o f coordinates. L e t us first see the b ehavior o f some dynam ical quantities
regarding reflection in a plane. Consider a particle A (F ig . 9 -1 6 (a )) m ovin g w ith
m om entum p . T h e m irror im age o f A is another particle A ' m ovin g w ith mo­
mentum p ' such that p j = pjj, p x = — pi., where Il and _L refer to directions
parallel and perpendicular to the plane, respectively. N e x t consider a particle
m ovin g as shown in Fig. 9 -1 6 (b ), w ith angular m om entum L . T h e m irror im age
o f A is another particle A ', rev o lvin g as shown in the figure and thus h avin g an
angular m om entum L ' such th at L\\ — — L [, L±. = L'±. W e see then th a t in
reflection in a plane, p and L behave in d ifferent ways. F or th at reason p is called
a polar v e c to r and L an a xia l vector. A ll vectors th at play a part in physical laws
are either polar or axial. T h e student m ay ve rify , b y exam ining Fig. 9-17, that
the electric field is polar and th at the m agnetic field is axial. Force is also a polar
vector.
 406 Fundamental particles (;9.6

M irro r M irro r

\
\
✓
* * ,
Ί <1

O riginal system M ir ro r im age

O riginal system M irro r im age
(a)

F ig. 9-17. Reflection in a plane of (a) electric field, (b) magnetic field.

T h e laws o f classical mechanics are in varian t rela tive to reflection; th a t is, to

the p arity operation P . In other words, if a given physical system satisfies the
classical laws o f m otion, its m irror im age also satisfies the laws o f m otion, and m ay
occur in nature. T h is means th at in the m athem atical statem ents o f classical
physical laws, polar and axial quantities m ust appear in such a w a y th at the rela­
tion am ong them is n ot changed b y space reflection. W e m ay then say that classi­
cal mechanics is invarian t to space reflection.
T h e law o f conservation o f parity states th at

parity is conserved in a process i f the m irro r image o f the process is

also a process which can occur in nature.

I t can be shown th at the M a x w ell equations for th e electrom agnetic field are
in varian t to space reflection, and th at therefore p a rity is conserved in electrom ag­
netic interactions. Physicists used to accept w ith ou t reservation the idea that all
interactions should conserve p arity, even in cases in which there was no direct
experim ental evidence to support the assumptions. So convinced were physicists
about this prop erty o f nature th at th ey were shocked when, in 1956, T . D. Lee
and C. N . Y a n g questioned the v a lid ity o f invariance under space reflection for
processes due to the w eak interaction. T h e Lee and Y'ang proposal was m otiv a te d
b y w h at at th at tim e was called the τ -θ puzzle: Each particle, described by its cor­
responding field or w ave function, is supposed to have a certain intrinsic parity.
T h e re are good reasons to assume th at mesons have negative p a rity (see E xam ple
9.5). L ook in g at T a b le 9-2, we see th at the (p ositive or n egative) kaon has, am ong
other possibilities, th e decay modes K i —» 27r± - f 7r~ and K i —> Jri + ir°. W e
can show (see E xam p le 9.0) that, if we assume th at each particle has a well-defined
p arity, then if p arity is conserved in the first kaon decay mode, it is not conserved
in the second, and conversely. T h e first d ecay m ode is called the τ -m ode o f decay
and the second the 0-mode (recall Figs. 9 -8 and 9 -9 ). A t the first appearance of
this dilemm a, physicists (to save the law o f conservation o f p a rity ) considered
th a t the tw o mesons m ight be different, each with its ow n parity, in spite o f the
9.6) invariance, symmetry, and conservation laws W7

.Mirror

F ig. 9-18. The 60Co experiment for

(C) ISO0 rotation o f system testing parity conservation in β-decav.

fact th at th ey were identical in all respects except the decay mode. Y a n g and
Lee proposed th at one should accept the idea th a t the tw o mesons were identical,
w ith w ell-defined parity, a t the expense o f overth row in g p arity conservation in
w eak interaction decay. T o test the conservation o f p a rity in processes due to
weak interactions, they also proposed several experim ents.
One o f the m ost famous experim ents was perform ed b y C. S. W u and her col­
laborators in 1907 at the N a tio n a l Bureau o f Standards. A sam ple o f 00C o was
polarized so th at the nuclei had th eir spins aligned (fo r which it was necessary to
place the sam ple in a strong m agnetic field and keep it at a tem perature close to
absolute zero). T h e n th ey found (as shown in Fig. 9 - lS a ) th at the electrons result­
ing from the β —-d ecay o f the 1,0C o nuclei were em itted in greater quantities in the
direction o f the C o spin (o r the direction o f polarization ) than in the opposite
.'i08 Fundamental particles ( 9.6

direction. T h is p roved that there is a larger p rob ab ility that a 00C o nucleus w ill
em it a decay electron in the direction o f its spin than in the opposite direction.
W h en th ey reversed the w hole system by rotatin g it through 180° around the
line L , the polarization, the spins, and the m agnetic field were reversed; the new
experim ental situation was as shown in F ig. 9 -1 8 (c ), w ith the direction o f m axi­
mum in ten sity o f electron emission also rotated 180°. On the other hand, the
m irror im age o f (a ) is shown in (b ), where the spins and the m agnetic field have
been reversed, because they are axial vectors, but the direction o f m axim um in­
tensity o f electron emission remains the same. C om parison o f (b ) and (c ) clearly
indicates th at (b ) does not correspond to a situation found in nature, thus p ro­
vid in g direct experim ental eviden ce that p arity is not conserved in weak inter­
actions, which are responsible fo r /!-decay. A fte r the fi0C o experim ent, m an y other
experim ental proofs w ere obtained for the nonconservation o f p arity in weak in ter­
actions. H ow ever, it seems th at in processes due to strong (as well as to electro­
m agn etic) interactions, p arity is conserved.
M irro r

Fig. 9-19. T h e n o n c o n s e rv a tio n o f

p a r ity in 7r-decay.

(a ) O rigin a l decay ( b ) S pace-reflected decay

A s a second exam ple o f the nonconservation o f p arity, consider the pion decay
7τ+ —» μ + + v, shown in Fig. t)-1 9 (a). T h e pion has zero spin and, in order to
conserve angular m om entum , the spins o f the muon and the neutrino m ust be in
opposite directions. Also, to conform w ith the h elicity o f th e neutrino, th eir spins
m ust be as indicated in the figure (also recall F ig. 9 -3 ). H ow ever, the m irror sys­
tem , shown in F ig. 9 -1 9 (b ), does not occur in nature because the neutrino would
have the w ron g helicity. A ctu a lly, physicists concluded that the neutrino has
n egative helicity because o f the fact th at in 7r+ -decay the μ + ’s consistently h a ve a
n egative h elicity. I f the neutrino could have either p ositive or n egative h elicity,
the μ + w ould also have positive or negative h elicity, in about the sam e proportion.
In such a case the m irror im age in Fig. 9-19 would correspond to an observed
process, and p arity w ould be conserved in pion decay. A ty p ica l experim ent by
which the h elicity o f the μ '1 is determ ined is shown in Fig. 9-20. T h e positrons
em itted in the μ + d eca y are alw ays m ovin g at alm ost 180° w ith respect to the origi­
nal m otion o f the μ + , and have p ositive h elicity (A = + 1 ). Thus, to conserve
angular m om entum , the helicity o f the other particles should be as shown.
9.6) Invariance, symmetry, and conservation laws W9

F ig. 9-20. Determination of the helicity of the μ +.

C h a rg e c o n ju g a t i o n . T h is operation consists in replacing all particles by

their antiparticles w ith ou t changing any other physical property, such as m om en­
tum or spin.

A system is invariant with regard to charge conjugation when, i f a process

is possible in the origin a l system, the corresponding process is also possi­
ble in the charge conjugate system.

I t seems th at processes due to strong and electrom agnetic interactions are in varian t
relative to charge conjugation, and this leads to the conservation o f T 2 and thus
also o f S.* H o w ever, processes in v o lvin g weak interactions are not in varian t rela­
tiv e to charge conjugation. T o use pion decay as an exam ple (F ig . 9-21 (a ) ) , the
charge conjugate system (F ig . 9-21 ( b ) ) cannot occur because the antineutrino
would have the w rong helicity.

F ig. 9-21. Application of charge

conjugation to the π-decay.

I Pr·

(a) Original decay (b) Charge conjugate decay

* Recent experiments, performed at Brookhaven and C E R N on the decay of η° into π°,

π +, and π - , have been analyzed for possible asymmetry in the behavior of the π + and
Tc . The experimental results have provoked discussions about the noninvariance of
electromagnetic interactions with respect to charge conjugation. The matter, however,
has not been settled at the time of this writing.
410 Fundamental particles (.9.6'
M irror

i Pe i Pμ ίΡ μ
H e lic ity I Ielicity
-I
9, <o»r s“ f j c C p , · +I

6-I
■*6 6-·
IPr
a, Pr

^n) O rigin a l decay (b ) Space-reflected decay (e) Charge conjugate o f (b )

F ig. 9-22. T he C P operation applied to τ -decay.

N evertheless, a comparison o f Figs. 9-19 and 9-21 suggests a new possibility.

Suppose th a t w e first perform a space reflection or p a rity operation P on th e sys­
tem shown in F ig. 9 - 2 1(a ) and then perform a subsequent charge conjugation C,
as*shown in F ig. 9 -2 2 ; the system resulting from the com bined operation (C P )
also occurs in nature; that is, π - —» μ ~ - f v. Thus:

W eak interactions are invariant under the combined C P operation.

T i m e r e v e r s a l. W h a t w ould happen if the direction o f flow o f tim e w ere

reversed? T h a t is, if t were changed in to — t, w ould the resulting equations still
describe possible processes? U n der tim e reversal the quantities ve loc ity , m o­
m entum , and angular m om entum are reversed and in a collision the initial and final
states are exchanged (F ig . 9 -2 3). Our intuition, supported b y strong experim ental
eviden ce both a t the m acroscopic and at the atom ic levels, points tow ard invariance
o f physical law s relative to tim e reversal. It is easily shown th at the laws o f classi­
cal m echanics and o f electrom agnetism are in varian t under tim e reversal. For
exam ple, dp/dl is in varian t under tim e reversal, since it implies the replacem ents
p —> — p and I —» — I. A lso the electric field £ is in varian t under tim e reversal;
how ever, the m agnetic field suffers the transform ation «B —» — (B because tim e re­
versal im plies reversing the velocities and therefore also the currents. T h en v X ®
is in varian t under tim e reversal, because both factors h ave changed sign, and the
equation o f m otion o f a charged particle, dp/dl = + υ X ® ), is invarian t w ith
respect to tim e reversal.
S trong and w eak interactions are also considered in varian t under tim e reversal,
although la te ly the problem has been open to discussion. R ecen t (19CG) experi­
m ents regarding a special form o f decay o f th e neutral kaon, which occurs in on ly
0 .3 % o f the cases, seem to indicate th at w eak interactions m ay v io la te the prin­
ciple o f invariance under tim e reversal.
9.6) Invariance, symmetry, and conservation laws ill

I*'ini>l sta te In itia l state

(a ) O riginal system (b ) T im e-rev erse d system

F ig. 9-23. T h e T o p e r a t io n .

W e shall conclude this section by stating another im portant theorem :

all physical laws are considered to be invariant under the C P T operation;

th at is, under the com bined operations o f tim e reversal T , p a rity P , and charge
conjugation C. T h is theorem is true even in cases in which the laws m ay not be
invarian t under the individual operations.

E X A M P L E 9.5. The parity of the pion.

S o lu tio n : Since the subject is interesting in relation to other calculations, we shall

illustrate how the parity of the pion is determined. Suppose that a beam of ir- -mesons
moves through liquid deuterium. Many pions, after they slow down, are captured by
deuterons and move in stationary states similar to electronic states. The systems thus
formed are called mcsic atoms. I f the mesie state is excited, the pions rapidly fall into the
Is ground state with radiation of energy. In the ground state the orbital angular mo­
mentum of the ττ~ is zero. Since the spin of the pion is zero, the total angular momentum
of the mesic atom is that of the deuteron; that is ,./ = I. The dimension of the Is orbit
of the π - is l/280th that of an electron Is orbit; there is thus a very large probability
that the pion will collide with the deuteron. The most probable reaction to occur is

x - + d + — 2n (J = I).

In this process angular momentum is conserved. Therefore the two resulting neutrons
must also have a total angular momentum of I. Hut the neutrons obey the exclusion
principle, and the complete wave function (orbital X spin) of the two neutrons must be
antisymmetric. The parity of the orbital wave functions is ( — 1)'. The two neutrons may
have their spins parallel (S - I ) or antiparallel (,S’ = 0). Spin functions for S = I are
symmetric and those for ,S = O are antisymmetric (remember Section 4.2). Then S = I
must be combined with an orbital angular momentum I — I, 3, 5, . . . odd and S = O
4/2 Fundamental particles (9.6

with Z = O12, 4, . . . even. The possible states of the two neutrons are then

5 - 1 : 3P 0, 3P i 13P 2l 3F 2 l3F 3l 3F 4, . . .
S = O: 1S0, 1D 2l 1G 4, . . . ,

where, as usual, the total angular momentum is indicated as a subscript. The only state
with J = I is 3P i 1 which must then be the state of the two neutrons, corresponding to
an orbital angular momentum of Zn = I.
L et us designate the parities of the three particles involved by P », P p, and P n, the orbital
angular momentum of the deuteron by Z4, and the orbital angular momentum of the two
neutrons by Zn. The parity of the left-hand side of the equation is P rP pP nC— l ) ' d and of
the right-hand side P n( — I ) 1". The conservation of parity in strong interactions requires
that
P . P PPn( - D ' 4 = P ? ( - D ' “ .

But the ground state of the deuteron has Z4 = 0 (with a small admixture of Z4 = 2; see
Section 7.7), and we have shown that In = I. Then P 1P p = — P n. I f we assume that
the proton and the neutron have the same parity (which is plausible, since they are dif­
ferent charge states of the nucleon), we conclude that P r = — I and the v ~ has odd
parity.
When we talk about the parity of the 7r°-meson, we need a slightly more complex
analysis, based on the fact that the 7r- + d + —> ir0 + 2n° process does not occur. The
result is consistent with an odd parity of the ir0 particle. AVe therefore conclude that all
pions have odd parity.

E X A M P L E 9.6. Lack of conservation of parity in the decay of the K-mcson.

S o lu tio n : Table 9-2 indicates that a K-meson can decay into either two or three pions.
As we mentioned previously, when these types of decay wrcre observed for the first time,
physicists assumed that these decays were due to two different mesons, called Θ- and r-
mesons, respectively. The decays were written as follows:

n 1JT+ + J T 0 + J T 0

Within experimental accuracy, the 9- and 7-mesons are identical, at least with respect to
mass, charge, spin, and lifetime; therefore the natural assumption was to consider them
as the same particle. The flaw in that assumption, in 1956, was that parity could not be
conserved in one decay if it were conserved in the other. W e shall now analyze this.
Working in the frame of reference of the decaying particle, let us call Se the value of the
spin of the 9+. Conservation of angular mbmentum requires that the total angular
momentum I of the system x + + jt° relative to the decay point also be Se; that is, I = sj.
On the other hand, the intrinsic parity of the pion is — I (see Example 9.5). Thus the
parity of the system Jr+ + π° is ( — 1)2( — I ) 1 = ( — I)*». Given that 1’« is the intrinsic
parity of the 0-meson and that parity is conserved in the O+ decay, we must then have

if Sj = 0
if Sj = I.

But there is strong evidence that Se = 0, and thus we should have Pj = + 1 .

9.6) Invariance, symmetry, and conservation laws 413

Lot us now consider the decay of the T+-particle, using a frame of reference attached
to the t + . W e shall designate the value of the spin of r + as sr. Using the decay scheme
T+ —> 7T+ -f- TT+ + TT- (the same result can be obtained using the other decay scheme
given above), we label the angular momentum of the π + -f- ir+ system relative to their
center of mass by I and use L to designate the angular momentum relative to the center
of mass of the whole system composed of the (tt + -f- ^ +) center of mass and the π - -
particle. The center of mass of the whole system coincides with the point at which the
decay of the t + takes place. Then the conservation of angular momentum requires that
l-\- L = Sr, and the quantum rule for addition of angular momenta requires that

\l - l\ < Sr < I + L.

On the other hand, the parity of the decay products is ( — 1)3( — 1 )'(— I)* - = — ( — 1),+Λ.
Thus if P r is the intrinsic parity of the τ -meson and if parity is conserved in the τ +-decay,
we must have

Pr = - ( — l ) ' + t .

Since it appears that the spin of the τ -meson is zero (sT = 0), we should have I = L and
thus I L = even integer, and therefore P r = — I. Thus if Sj = sr = 0, we have
that P» = — P r and the two particles do not have the same parity. (I f s* = sr = I, we
reach the same conclusion after a more elaborate consideration.) Therefore the assump­
tion that Θ and τ particles are the same implies that the law of parity conservation has
been violated in one of the two decays.

I S(H) (2 +)
IS(H)
1120(2 · I 1 4 2 0 (0 -)

1 3 1 0 (2 -) 1310(1 +)
12X5(1 · )
121 0 ( 1 +)
1250(2 - )

IOSOd η
IOSO(O+)
1003 (O +)
KHHl 1019(1 - )
I n
990(1 +)
S92 ( I * )
> 958 (0 —)
"Τ'. - 7 (5 0 (1 ") 7 X 3 (1 - )

5 4 8 (1 )-)
4 9 6 (0 - )
S(H)

Fig. 9-24. Meson resonances. The

1 3 7 (0 -) spin and parity of each resonance is
given in parentheses.

K I
*-0 y= T I D -O
T= I r=i T=O
7= ± 1,0 7= - 1, 0 7= 0
41‘4 Fundamental particles (,9.7

I 2 1 9 0 (4 " )

2100 (|-)

2030 (4-)
2000
I 9 2 0 ( | 1910( 4- )

ls 3 ° ( i T ) I SI 5 (?)
1815 ( 4 + ) 1 7 6 7 (j-)

1674 ( j j H
»«™»*~> I6TOJ Q 1660(|-)
1670(§ ~ )
1 5 7 0 (1 " )
1 5 2 0 (4 " ) 1 5 2 0 (1 ") 1 5 3 0 (4 -)
. 1500

1-100 (4^) 1 4 0 5 (4 " )

1385(4 - )

131 8 (4 -

1230 ( j +)
1 1 9 3 (4 - )

1115(4 - )

1000
9 3 9 (4 - )

800
N Δ Λ S Ξ il
!/ = + 1 V= + 1 V= O y= 0 v= —l I / = —2
T= 4 T“ 4 r= 0 T=I r= 4 T = O
7= 4- 1, 0 7= 4- 2, ±1, 7= 0 7= ± 1, 0 7= — 1, 0 7= —I
0
F ig. 9-25. Baryon resonances. The spin and parity of each resonance is given in
parentheses.

ft. 7 K eson a n ees

T h e fundam ental particles listed in T a b le Q -I can all be considered lon g-lived b y
particle standards. In addition to these lon g-lived particles, in the last fe w years
experim ental evidence has accum ulated which points tow ard the existence o f v e r y
short-lived particles, called resonances. T h e ir lifetim es are so short (o f the order o f
IO-2 0 s or less) th at th ey do not leave any recognizable track in bubble or spark
chambers. T h ese particles can be classified according to baryon number, hyp er­
charge, and isotopic spin, and are designated b y the same sym bols as those baryons
and mesons which have the same quantum numbers as the resonances, but w ith a
subscript I, 2, 3, . . . according to increasing mass. T h e number o f such resonances
is about 80 i f one includes all charge states and anti particles; th eir num ber is in­
creasing continually. Figure 9-24 (sec preceding p age) shows som e meson re­
sonances and F ig. 9-25 gives some o f the known baryon resonances. T h e masses
(in M e V ), spins, and parities arc also shown.
9.7) Resonances 4/5

(a) F ig u re 9—26

F ig u re 9-27

Resonances are identified by a v e ry subtle application o f the principles of con­

servation o f energy and m om entum . Suppose th at a particle A collides w ith an­
other particle B at rest in the laboratory, resulting in particles I, 2, 3 (F ig . 9 - 2 6 (a ));
th at is, A + B —i> I + 2 + 3. I f we observe particle I at a given angle w ith respect
to the direction o f m otion o f A , we should observe a continuous energy spectrum,
since the conservation o f energy and m om entum allows d ifferent directions o f
m otion and different energies o f particles 2 and 3 fo r a given direction o f m otion
o f I. Suppose, instead, th a t the process is in tw o steps. In the first step, on ly tw o
particles are produced; th at is, A - f B —* I + C. In the second step, particle C
decays into 2 and 3; that is, C - * 2 + 3 (F ig . 9 - 2 6 (b )). Since the first process
in volves on ly tw o particles, the energy o f p article I is fixed for a g iven direction
o f m otion and its energy spectrum is as shown in the figure. In this case the energy
o f particles 2 + 3 is also fixed. F igu re 9-27 shows a m ore com plex situation, in
which five particles are produced. I f particles 3, 4, and 5 result from the decay
ά16 Fundamenlal particles

Fig. 9-28. Production of the η° resonance in a proton-antiproton annihilation. (Photo­

graph courtesy the University of California Lawrence Radiation Laboratory, Berkeley,
California)

of an intermediate particle C 1 there must be a certain correlation among their

energies. Therefore, by analyzing the energy of the particles resulting from a
collision, we are able to determine whether the process occurs in one step or in two
steps.
T h e first resonance that was discovered (about 1960) was the 770 (originally
called ω °). Its discovery came about as a result of the analysis of proton-antiproton
annihilation observed in the Berkeley bubble chamber. One of these annihilations
is shown in Fig. 9-28. I t corresponds to the production of five pions,

P + + P - —■» 27T+ + 2 tt~ + 7Γ0·

O f course, the 7r° is not visible, but we can infer its existence from momentum
and energy conservation. T h e process can be represented as in the drawing in
Fig. 9-28. B y analyzing the energies of the mesons by means of this and many
other similar processes, we can conclude that three of the mesons [in our case those
marked ( I ) , (3), and (5)] proceed from the decay of a short-lived particle having
a rest mass of about 548 M e V , and thus is one of the 77-mesons, d e sig n a te d ^ 0.
Thus, instead of the above scheme, we must write

0
P r TT+ H 7T -

— » 7T+ - - 7 r 4 TT0

This is the w ay the process is represented in Fig. 9-29. N o te that even if the
77°-meson is m oving at the velocity of light (3 X IO 8 111 s—*), in its lifetim e

(~ 1 0 _ 2 0 s) it cannot m ove more than 3 X 10“ 1 2 m, a quantity impossible to

measure in a bubble-chamber photograph.
9.7) Resonances

Fig. 9-29. Interaction region of process

illustrated in Fig. 9-28, magnified about
IO13 times.

R esonances d eca y b y means of strong interactions, w hich accounts for their ex;
trem ely short lives. Som e observed decays are:

M eson s B aryons
&
+ TT0 + + 0 N i +
TT n ; P 7Γ —^ t; 0 - f - 7Γ
+ 0
V01 - ■» 7Γ 7T
I

Γ TT
_ 0

Λ® * S 0 + TT0 A 2 * Σ+ 4 7Γ
0 + Δ ++ P + + TT+
KJ K + + TT A 0 + 7T +

T h e student should apply the conservation laws to these decays to find w hich, if
any, laws are violated, and should give reasons w hy it is possible for these decays
to occu r b y m eans o f strong interactions.

E X A M P L E 9.7. Calculation of the energy spread, in the laboratory, of the two photons
that result from the decay of a 7r°-meson with a total energy E ir relative to the L-frame.
S o lu tio n : Let us consider a 7r°-meson with energy E ir and momentum relative to the
laboratory or L-frame. Then E ir = cv mlc2 + p\. The velocity of the meson (see
Appendix I, Eq. A. 10) is

v — C2P ir/ E ir. (9.12)

This is also the velocity, relative to the L-frame, of the C-frame, in which the 7r° is at
rest. In the C-frame the two photons resulting in the decay —» 7 + Ύ are emitted in
opposite directions with an energy Ell — ^mirC2 and a momentum = EliZc —
Due to the symmetry in the C-frame, the photons are emitted isotropically. But this is
not the case in the L-frame, in which the forward direction is preferred because of the
motion of the C-frame.
Due to the Doppler effect, the energy of the photons in the C- and L-frames is not the
same. In general, the two photons do not have the same energy in the L-frame. The
maximum energy spread occurs when one photon is emitted in the direction of ρ π (or
forward) and the other in the opposite direction (or backward). Then it is simple to com­
pute the energy of the two photons in the L-frame. If i is the energy of the forward
photon and E y 2that of the backward photon, their respective momenta, in the direct
O fp7r, are py1 = E y\/c and py2 = —E y2/c. Conservation of energy and. momentum give

E ir = E y1 -T E y2 , Pir E yi/c (9.13)

so that
Eyl = h
(E
v
0 P tt)
and E y2 = ^ (E ir - cpw) (9.14)

Thus the energies of the photons in the L-frame have a spread A E = E y\ — E y2 = Cpir
418 Fundamenlal particles (9.7

W e shall now apply these formulas to a particular situation. It is observed that, in a

7r- -p + collision, the end products are often a neutron and two photons; therefore we may
write the reaction as

TT- + p + - m + Ύ + 7. (9.15)

If thisreaction occurs in one step (i.e., if itcorresponds to Fig.9~2G(a)with proper iden­

tification of the particles), it is a three-body problem.Assuming that the ir~ and the p +
are both at rest in the laboratory, the total energy available is

Q = (τη ,- + /ηp — rnn)c2 = 139 MeV.

This energy must appear as kinetic energy of the three resulting particles. Since this
energy can be distributed in a continuous way among the three particles, the photons
could have any energy from zero to almost 139 M cV.
Another alternative process is one which occurs in two steps; that is,

a·- -)- p + —» n -(- Tr0

U 7 -I-7 (9.16)
a
corresponding to Fig. 9-26(b). In this case the energy released (if the 7r- and p + are both
at rest in the Λ-frame) Is

Q = (?n,_ - f i n , - /Hn — ntro)c'2 — 4 M eV.

This energy appears as kinetic energy of the n and tt°; therefore, according to the laws of
conservation of energy and momentum (see Appendix II, Eq. A .27), the kinetic energy
of the Tr0 is

E„.w» = ---------- Q ~ 3.6 MeV.

THn + TH» 0

W e have used a nonrelativistic formula, since the kinetic energy of the pion is much smaller
than its rest mass. Therefore the total energy of the 7r° is about 138.6 M e V , corresponding
to cpr ~ 31 M e V , which would be the energy spread of the photons resulting from the
pion decay. The photon energies should then fall in the range £(138.6 ± 31) M eV or
from F y2 ~ 54 M eV to F y\ ~ 85 M eV. This is what is observed experimentally, verify­
ing that the ττ- - ρ + collision is a two-step process that takes place according to Eq. (9.16).
This example, therefore, illustrates what we have said about identifying resonances by
means of cnergy-momentum correlations.

E X A M P L E 9.8. Detection of the j)°-particle.

S o lu tio n : The 7/°-particle, as we explained in connection with Figs. 9-28 and 9-29, has
such a short life that it cannot leave measurable tracks in a bubble chamber. In that
respect the ij°-particle behaves like a resonance. Let us consider the reaction

τγ+ 4 - Ρ + ^ Ρ + + τγ+ -(- τγ+ + τγ- + TT0 .

I f all the pions are produced at the time of the collision, the process would correspond to
Fig. 9-27(a), with no correlation among the energy and momentum of the five particles
except that imposed by the overall conservation laws. Hut the possibility exists that the
9.8) Whal is a Jimdamenlal particle? 419

process occurs in two steps,

-TT+ + P + ~ * P + 4" JT+ 4* V 0

U π+ + T T - + 4 '

corresponding to Fig. 9 -27(b). In this case the energy and momentum of the three parti­
cles resulting from the »)0-deeay must be consistent with those of a particle of given
mass. Noting that in this case we must have

E r + E p ^ E'p + E ', + E „

P r + P v —» P p + P r + P „

we may experimentally determine. /?, and p , by measuring the other quantities, and from
those values we should be able to obtain the mass of the η°. The difficulty is that we ob­
serve two 7t+ and we cannot tell which one is the original ir+ and which one comes from
the η0. Therefore, we have to make the mass calculations for the η ° in duplicate, using
both 7r+’s. The experimental result is shown in Fig. 9-30. The pronounced peak around
a mass equivalent to 550 M e V , corresponding to the correct 7r+, is proof that the process
has two steps involving an jj°-particle of such a mass. The remainder of the mass dis­
tribution is due to the wrong choice of a x + in each case. Thus we again see how the con­
servation laws allow us to infer the existence of particles which we cannot observe other­
wise.

F ig. 9-30. Experimental mass of the

intermediate ij° resonance. I f this particle
did not exist, a mass distribution without
peaks would be observed.

Mass of intermediate particle

9.11 W h a t is a FuntliinutIiIuI I tIirIit-It t?

N ow , in light o f our preceding discussion, are we in a position to define a funda­
mental particle? W e know that fundamental particles are precise physical entities
characterized by certain properties such as charge, mass, spin, etc., that these
particles interact am ong themselves according to more or less well-defined inter­
actions (strong, electromagnetic, weak, and gravitational), and that all the pro­
cesses which take place am ong these particles follow certain conservation laws.
But there are still many serious and im portant questions. W h y are there so m any
particles? W h at function in nature does each o f them fulfill? H ow are they related
am ong themselves? W h y do they have certain mass and spin values? W hy are
they divided into tw o very distinct classes, bosons and fermions?
420 Fundamental particles

X10-* Χ Ι0-*
ε
O 2.0 O 2.0

ιΟ.ό 1.0 / 1.5 2.0 2.5Χ IO-15 ιη

(a) Proton (O) Neutron

F ig. 9-31. Theoretical radial charge distribution for (a) protons, (b) neutrons.

In the same w ay th at we look a t atom s as being com posed o f certain basic in­
gredients (electrons, protons, and neutrons) or o f nuclei as being com posed o f
protons and neutrons, w e m ay assume th at all fundam ental particles are composed
o f certain building blocks or superfundam ental particles. G ell-M a n n has proposed
the name quark for these superfundam ental particles.* Quarks have certain novel
properties, such as fractional charge (J-e or § e ). B u t as y et nobody has observed
quarks, in spite o f the intensive hunt th at has been g oin g on. F ollow in g another
approach, tve could consider, for exam ple, all baryons and th eir resonances to be
excited states o f a basic baryon (w e m ight use a sim ilar logic for mesons) in the
same w a y th at a hydrogen atom m ay exist in its ground state or in m any excited
states, each state havin g its ow n attributes, such as energy, angular m om entum ,
and p arity. B u t no satisfactory th eory along this line has y e t been form ulated.
In any case, w hat we call fundam ental particles do n ot seem to be b y any means
sim ple entities. F o r m any years physicists h ave considered a nucleon as being
com posed o f a core— a “ b a re ” nucleon which is unobservable— surrounded b y a
cloud o f pions, in the same w ay th at an atom is a nucleus surrounded b y a cloud
o f electrons. T h e radial charge distribution o f this p ion cloud for the proton and
the neutron could be as illustrated in Fig. 9-31. F o r the neutron, the total charge
is zero. (In cid en tally , this affords a means o f distinguishing a neutron from an
antineutron, since the antineutron would have the sign o f the different layers o f
charge reversed.) T h ese graphs are sim ilar to those o f Fig. 3-13 fo r the radial

* The word was taken from a rather obscure passage of James Joyce’s Finnegan’s Jl'afce:

Three quarks for Muster Mark!

Sure he hasn’ t got much of a bark
And sure any he has it ’s all beside the mark.

Webster’s New International Dictionary, 1961, defines “quark” as the harsh cry of the
crow, or any sound im itative of this cry.
9.8) Whal is a fundamental particle? 421

Fig. 9-32. Strong interaction resulting from the exchange of pions.

charge distribution o f an electron in an atom. N o theory abou t pion dynam ics in

a nucleon has y e t been developed, but ap p aren tly the pion cloud m ay be excited
to higher energy levels, g ivin g rise to nucleon isobars, in the same w ay that atom s
m ay exist in excited electronic states.
A n oth er interesting aspect is the interpretation o f interactions as the result o f
the exchange o f bosons betw een the interactin g particles. A n electrom agnetic
interaction results from the exchange o f photons between tw o charged particles,
as indicated in Fig. 1-13. Sim ilarly, it is accepted th at the strong interaction is the
result o f an exchange o f pions between the in teractin g particles, as indicated in
F ig. 9-32. T h e particles exchanged are called virtual because th ey cannot be de­
tected as separate entities. T h e short range o f nuclear forces m ay be v e ry nicely
explained w ith this m odel fo r interactions. A proton is not a static system, but is
continuously ejectin g and reabsorbing some o f its surrounding pions. W hen a
virtual pion is em itted, the proton energy changes by an am ount

A E ~ Uit Ci ~ 140 M eV .

A ccord in g to H eisen berg’s uncertainty principle, E q. (1.49), this pion can exist,
w ith ou t any violation o f the laws o f quantum mechanics, during a tim e

At ~ h /A E ~ Iifm 1C i ~ IO-22 s.

A fte r this tim e the virtu al pion must be reabsorbed b y the nucleon or exchanged
w ith another nucleon. In this tim e, if we assume that the pion travels w ith a
v e lo c ity close to that o f light, the m axim um distance it can go is about IO -14 m.
T h is then gives th e m axim um distance at which a second nucleon must be located
to absorb the virtu al pion. T h e student should be struck b y the fact th a t this is
precisely the m agnitude o f the range o f the nuclear interaction. W h en we think
about the ab ove m odel o f nucleons and their interactions, w e sec th at it is an o v e r­
sim plification to say th at a nucleus is com posed o f protons and neutrons. The
best indication th at a bound neutron is not the same as a free neutron is that
bound neutrons in general are stable and do not decay.
In the case o f electrom agnetic interactions, we m ay assume th at a charged par­
ticle is continuously e m ittin g and absorbing virtu al photons. T h e virtu al photons
em itted by charged particles have zero rest mass; therefore the energy fluctuation
A E o f a charged particle m ay have an y arb itrary value, and the length o f tim e th at
the virtu al photon can exist before it is reabsorbed or exchanged w ith another
charged particle is also arbitrary. A calculation shows th a t the force between tw o
422 Fundamental particles

charged particles resulting from the exchange of zero-rcst-mass photons must vary
as the inverse square o f the distance o f the tw o charges, in agreement with C ou­
lom b’s law.
I t thus appears th at pions are the carriers o f the strong interaction. F o r this
reason the existence o f the g raviton as the carrier o f gravitation al interaction has
been postulated, and another p article (a w eak boson, W ) has been postulated as
the carrier o f the w eak interactions. N eith e r o f these particles has y e t been
observed.
Alth ough the th eory o f elem entary particles is still in an im perfect state, phys­
icists have been able (b y using some elaborate m athem atical concepts) to gain
some understanding o f the relations am ong the particles. Perhaps the m ost in­
teresting th eory is one proposed in 19G1 b y M . G ell-M a n n and Y . N e ’eman, called
the eightfold way because it required a set o f eigh t basic operators. T h is th eory
predicts that, am ong the baryons and mesons, m ultiplets o f eight and ten particles
should exist w ith certain relations between their quantum numbers and their masses.
O ther groups w ith a larger number o f particles are also supposed to exist. The
theory predicted the existence o f the Ω- -particle, which was shortly afterw ard
observed (F eb ru ary 19G4) at B rookhaven N ation al L ab orato ry (see E xam p le 9.10).
T h e field o f elem entary particles is one o f the m ost active and challenging areas
o f research in contem porary physics. N e w and bigger accelerators are constantly
being built to exam ine the existing problems, but these accelerators often create
new problem s b y uncovering new and unsuspected processes. I t is hoped, how ever,
th at in a few years our understanding o f elem entary particles w ill reach a status
sim ilar to our understanding o f nuclei, atoms, and molecules.

E X A M P L E 9.9. Inelastic scattering of high-energy protons as a result of proton-proton

collisions.

F ig. 9-33. (a) Schematic diagram of proton-proton inelastic scattering experiment,

(b ) Experimental results showing inelastic scattering peaks.
 9.8) H7Zia/ is a Jundamenlal particle? 423

S o lu tio n : An important experiment showing the existence of nucleon excited states

(that is, nucleon isobars in which the pion cloud has been raised to an excited energy
state) is the analysis of proton-proton collisions. The experimental setup appears
in Fig. !>-33(a). Protons from an accelerator hit a liquid-hydrogen target. Those
protons which are scattered through a fixed angle Θ pass through a magnetic field (B,
which deflects some of the protons through an arc of a circle of fixed radius r, determined
by the initial direction of motion and the position of the detectors Di and D i- This allows
us to determine the momentum of these protons, given by p — efflr. Hy varying the in­
tensity of the magnetic field, we can change the momentum of the protons passing through
the fixed detectors and analyze the momentum distribution of the scattered protons. The
experimental result is shown in Fig. 9-33(b). In addition to a main peak in the momentum
distribution of the protons (corresponding to elastic scattering by the target), there are
several secondary peaks, corresponding to protons of lesser momentum or kinetic energy.
These secondary peaks correspond to inelastic scattering, in which the incoming protons
lose some of their kinetic energy to a target proton, which is raised to an excited isobaric
state of well-defined energy. The student may recognize the fact that this experiment is
similar to the Franck and Hertz experiment of inelastic clectron-atom collision, which
showed the existence of excited stationary atomic states of well-defined energy.

E X A M P L E 9.10. The omega-minus experiment.

S o lu tio n : According to the “ eightfold w ay” theory of Gell-Mann, particles should be

grouped in families, with all members of a family having the same spin and parity. If
we look at the resonances shown in Fig. 9-25 and plot the family of ten lighter particles
having spin § (and positive parity), we obtain the arrangement of Fig. 9-34, which ex-
Mass, MeV
Isotopic spin r
Strangeness
n-
3 - - I)

2 ----- 4 1530

I I 1385

A »/ I* /
I) § 123S
JA - J -A L
-I ■I / - i O / J I / i
/ / /
q/e = - I (I +1 +2
F ig. 9-34. Arrangement of lighter hyperons with spin § and positive parity, following
Gell-Mann’s eightfold way.
424 Fundamental particles C9.8

liibits a nice geometrical symmetry. A t the time of Gell-Mann’s proposal (1961), only
the Δ -quartet and the Δ -triplet were known. But shortly afterward (1962), the S-doublet
was reported, and it fitted well with the scheme. From the regularity of the pyramidal
structure it was easy to predict that the remaining particle at the top should have T1 = 0
and r = 0, and thus be a singlet. Also its strangeness should be i = —3, giving a charge
— e according to Eq. (9.11). Finally, from the regularity in the mass differences Δ — Σ
and Σ — Ξ, it could be inferred that the new particle (called Ω“ by Gell-Mann) should
have a mass about 1675 MeV. This therefore fully identified the missing particle. (Gell-
Mann’s prediction was based on a more serious theoretical basis than this simple
geometrical arrangement.) From these properties experimenters expected, in view of the
conservation laws, that the Ω“ could decay into H0 + ιτ“ , Ξ “ -I- ir0, or A 0 -f- K - ; this
meant that, by observing the decay products, they had a clue by which they could
identify this particle.

F ig. 9-33. Schematic diagram of the Ω experiment. Before the separation there were
approximately SOO x “ and IO p “ for every IO K - particles. After separation, there was
only one x “ and no p “ for every 10 K “ -particles.

The next step was to see if the particle could be produced and observed in the laboratory.
A possible production process, compatible with the conservation laws, would be

K - + p + —. Ω " + K + + K 0.

In 1963 an experimental setup was prepared at the Brookhaven National Laboratory.

A 33-GeV proton beam generated by the accelerator hit a tungsten target, producing
K "-mesons, together with pions, autiprotons, and other particles. T o extract the K “ -
mesons, the experimenters devised an ingenious arrangement, shown in simplified form
in Fig. 9-35. For experimental convenience, they chose K _ ’s with a kinetic energy of
5.0 GeV (which is well above the threshold energy of 3.2 M eV of the. process) and ex­
tracted them from the accelerator tube by means of a deflecting magnet. The extracted
beam, in addition to containing K “ -particles, was composed of a large number of x “
and a few jp“ , so the next task was to separate the K “ -particles from the other particles.
This was accomplished by means of a second set of deflecting and separating magnets,
together with a slit arrangement. N ext they allowed the almost pure K “ -beam (it con­
tained only about 10 percent x “ and no antiprotons) to enter a shielded 2-m bubble
chamber containing liquid hydrogen, in which the reaction producing the Ω“ could take
place. The total length of the path of the K “ ’s from the target to the bubble chamber
was about 135 m. A fter a run of several weeks, by the end of January 1964 the experi-
9.8) Whal is a fundamental particle? 425

(») <b)
F ig. 9-36. Photograph which first showed Ω - particle production. (Photograph courtesy
Brookhaven National Laboratory)

menters had obtained about 50,000 photographs, of which one (shown in Fig. 9-36)
corresponded to a process in which an Ω- had been produced. The trend of processes in
Fig. 9-36 is as follows:

Κ " + p+ - * Ω - + K + + K 0 (V e rte x F )
^->Ξ0 + π - (V e rte x F )
U A0 + y + T (Vertex D )

L. L->c+ + e “
e + + e~
(V ertex C )
(V e rte x F )
(Vertex /I)

Of course the neutral particles do not leave any track in the chamber. The photograph
is analyzed at the right in Fig. 9-36(b). From vertices A, It, and C the energies, momenta,
and directions of motion of the A 0 and the two 7 ’s arc found, thus locating vertex I ) and
the energy, momentum and direction of motion of the H0. Finally, using the previous infor­
mation, the experimenters could compute the energy and momentum of the Ω- from the
data at vertex E . The analysis gave a mass value between 1668 M eV and 1686 M eV.
A second photograph, obtained a few weeks later, narrowed the mass to the range
between 1671 and 1677 M eV , in excellent agreement with the theoretical prediction.
The length of the Ω--path in the chamber was about 2.5 cm, showing that the Ω-"-life­
time is about 2.5 X IO-2 m/3 X IO8 m s 1_ ~ IO-10 s.
 nl particles

1. "Evolution of the Physicist’s Picture of Nature,” P. Dirac, Sci. Am ., M ay 1963,

page 45 «
2. “ Early Work on the Positron and M uon,” C. Anderson, Am. J. Phys. 29, 825 (1961)
3. “ The Role of Elementary Particle Research in the Development of Modern Physics,”
V. Weisskopf, Physics Today, June 1963, page 26
4. “ Particles and Principles,” M . Gell-Mann, Physics Today, November 1964, page 22
5. “ Thirty Years of Meson Physics,” R. Oppenheimer, Physics Today, November 1966,
page 51
6. “ Resource Letter S A P-I on Subatomic Particles,” C. Swartz, Am. J . Phys. 34, 1079
(1966)
7. “ The Conservation Laws of Physics,” G. Feinberg and M . Goldhaber, Sci. Am.,
October 1963, page 33
8. “ Violation of Symmetry in Physics,” E. Wigner, Sci. Am ., December 1965, page 28
9. “ Resonance Particles,” P. Hill, Sci. Am ., January 1963, page 38
10. “ Quarkways to Particle Sym m etry,” L. Brown, Physics Today, February 1966,
page 44
11. “ Unified Theories of Elementary Particles,” S. Blackman, Physics Today, February
1966, page 55
12. Structure of Matter, W . Finkelnburg. N ew Y ork: Academic Press, 1964, Chapter 5,
Sections 20-26
13. “ Symmetry and Conservation Laws,” E. Wigner and “ Elementary Particles,” G.
Chew, published in The Scientific Endeavor. New Y ork : Rockefeller Institute, 1965
14. The Feynman Lectures on Physics, Volume I, R. Feynman, R. Leighton, and M.
Sands. Reading, Mass.: Addison-Wesley, 1963, Chapter 52
15. The Fundamental Particles, C. Swartz. Reading, Mass.: Addison-Wesley, 1965
16. Elementary Particles, D. Frisch and A. Thorndike. New Y ork: Momentum Books,
Van Nostrand, 1964
17. Particles and Accelerators, R. Gouiran, World University Library. New Y ork:
McGraw-Hill, 1967

l*roblvniM

9.1 Compute the radius, energy, and
angular velocity of the ground-state orbit
of positronium. Also determine the first
excitation energy of positronium. How
many revolutions will positronium make,
on the average, before annihilating, if it
is in (a) the singlet state, (b) the triplet
state?
9.2 Muonium is formed when a charged
μ-meson and an electron or positron cir­
culate about each other. Determine (a)
the energy and radius of muonium in its
ground state; (b) the dissociation energy
of muonium.
9.3 A negative pion may be captured into
a stable orbit around the nucleus, con­

stituting a mesic atom. Assume that we
can compute the energy and the radius of
the mcsonic orbit by the same formulas
used for electronic orbits in the hydrogen
atom (Example 3.1). (a) V h a t energy is
released when a free pion at rest is cap­
tured into the ground state around a
proton? (b) Compute the radius of the
ground-state orbit of a pion moving around
a proton, (c) Estimate the nucleus for
which the radius of the ground-state or­
bit of the pion is equal to the radius of the
nucleus.
9.4 A neutral kaon with a kinetic energy
o f 100 M eV decays in flight into two op­
positely charged pions. The kinetic energy
of one of the pions is 200 M eV. Compute
the momentum of each pion and the angles
their paths make in the Λ-frame.
9.5 A neutral K°-meson is observed to
decay into a pair of oppositely charged
pions. Initially the pion tracks are per­
pendicular in the Λ-frame, but are bent by
a magnetic field of 8.5 X IO-1 T , so that
they have radii of 0.8 in and 1.6 m, respec­
tively. Calculate the rest mass of the K 0-
meson and its kinetic energy.
9.6 Determine the Q-value and the pro­
jectile threshold energy in the Λ-frame for
the following reactions:
x - + p + - A 0 + K 0,
p + + p+ _> p + + n 4. π + '
p + + p + _ ρ+ + Λ0 + K +.
In each case the projectile is the first
particle. The second particle is the target,
assumed at rest in the laboratory.
9.7 Calculate the minimum kinetic energy
of the incoming proton necessary to trigger
the process shown in Fig. 9-12.
9.8 Determine the energy of the photon
in the process x “ + p + —>n + 7, when
both colliding particles are at rest.
9.9 W hat is the threshold kinetic energy
of the incoming particle for the processes
illustrated in Figs. 9-10 and 9-11?
Problems 427
9.10 Find the magnetic field for the chosen
value of the p _ -momentum in the anti­
proton experiment (Example 9.2).
9.11 In the x ° —* 7 + 7 process, consider
the case in which the two photons are
emitted in the C-frame in a direction per­
pendicular to ρ , (in the Λ-frame). Show
that in the Λ-framc their energies are \ E ,
and that they move at an angle with p ,
given by tan-1 w ,c/p,.
9.12 A X 0-In e so n having a kinetic energy
in the Λ-frame equal to its rest energy de­
cays into two photons. Suppose that, in
the C-frame, the photons are emitted at
angles of 30° and 210°, respectively, with
the direction of motion of the x ° in the L -
frame. VVhat are their energies and the
angle made by their directions of motion
in the Λ-frame?
9.13 Consider the decay of a x°-meson
into two photons. Given that the photon
energies are E i and E 2, show that they arc
related by
E i E 2 = ^(m »c2) 2/(I — cos 0),
where 0 is the angle between the photon
directions as measured in the Λ-frame.
9.14 A beam of negative pions (x ~ ) enter­
ing a bubble chamber triggers the reaction
χ - + p + —* A 0 + K 0. The successive
decay processes of A 0 and K 0 also take
place within the chamber. A magnetic
field is applied in the region occupied by
the chamber. Make a diagram showing
the whole process. Neutral particles
should be represented by dashed lines and
charged particles by continuous lines with
the proper curvature.
9.15 A I-M c V positron collides with an
electron which is at rest in the Λ-frame
and the two annihilate, (a) W hat is the
energy, in the C-frame, of the two photons
emitted? (b) Given that one photon is
emitted in the direction of motion of the
positron and the other in the opposite
direction, find their energies in the L -
frame.
428 Fundamental particles
9.16 The annihilation probability per unit
time of positrons is λ = 7.48 X 10- l5 n s -1 ,
where n is the number of electrons per unit
volume. Show that the hgjf-life of positrons
moving through argon (Z = 18) is T =
2.67 X 10~"/p, where p is the pressure,
in atmospheres, of argon.
9.17 Protons may be accelerated to an
energy of 33 GeV in the Brookhaven alter-
nating-gradient synchrotron (A G S ), (a)
W hat energy is available for reactions
with the protons (at rest in the Λ-frame)
in llrookhaven’s hydrogen bubble cham­
ber? (b) What energy is available if the
protons are stored in a circular ring and
arc allowed to react with a ring of stored
protons of the same energy which are cir­
culating in the opposite direction?
9.18 A IOO-MeV π-meson decays, pro­
ducing a μ-mcson emitted in the forward
direction. Calculate the kinetic energy of
the μ-meson in the Λ-frame.
9.19 Calculate the energy of the photon
emitted when a 2°-particle, at rest in the
Λ-frame, decays to a A°-particlc.
9.20 By application of the Lorentz trans­
formation for energy and momentum
(Appendix I, Eq. A .16), obtain Eqs. (9.14),
which relate the energy and momentum of
the photons in the C- and Λ-frames. (Take
the X-axis parallel to the relative velocity
which is given by Eq. 9.12).
9.21 Considering the process 7r- + p + —>
A0 K 01(a) what are the possible values of
T for the two reacting particles and for
the two resulting particles? Determine the
value of T for conservation of isotopic spin.
Also determine whether T , and S are con­
served. (b) Repeat the analysis for the
process ir~ + p + —> A 0 + π° and conclude
if the process is expected to occur in nature.
9.22 Consider the process p + + p + —>
p + -f- n + -Jr+ . Determine the total iso­
topic spin; are T . and strangeness con­
served? Repeat for P + T P + - 1 P t T
n + e + + ve. This process occurs with a
much lower probability than the first-
mentioned process. W hy?
9.23 Check the several conservation laws
(except energy, momentum, and angular
momentum) in the following strong inter­
action processes.
(a) p + + p+ - * p+ + A 0 -E K +
(b ) T T ~ -\- P + - * 2 ° + K 0
(c) p + + p + - » E 0 + p + + K 0 + K +
(d) A 0 + p + -> n + p+ + K 0
(e) K - + P + - * K + + S -
Determine in each case the values of T ll
T , and S for the reacting and resulting
particles.
9.24 W:hich conservation laws are satisfied
and which are violated in processes
Ij0 —* p + + e “ and π° —> 7 + 7?
W hy is it that 2 ° —» A 0 + 7 occurs, but
2 + —» p + + 7 is not observed? W hy is it
that Ξ - —> A 0 + i r _ occurs, but Ξ - —*
η° + ir_ is not observed?
9.25 Analyze the process K - + p + —*
Ω- + Κ + + Κ ° from the point of view
of the conservation laws. Calculate the
threshold kinetic energy of the K - -
particle.
9.26 Show that the processes ir- + p + —>
n + 7, Tc- + d —* 2n + 7, and T + + d —*
2p+ all imply that the spin of the pion is
either 0 or I. (Sec the following problem.)
9.27 Let us designate by σ ι the cross sec­
tion for the process p+ + p + —* t r + + d
and by σ 2 the cross section for the inverse
process π + + d —> p + + p + . W e can
show that the cross sections are related by
<n = $ (p r / P p )2 (2 s r + 1)σ2,
where p , and pp are the momentum of the
incoming pion or proton in the C-frame of
reference and s , is the spin of the pion.
I t has been found experimentally that
σι = 0.18 mb for protons with an energy
of 340 M eV in the Λ-frame and σ τ — 3.1 mb
for pions with an energy of 29 M eV in the
Λ-frame. Verify that these experimental
results are consistent with s , = 0 but not
with s , = I. [H in t: In finding p r and pp

in the C-frame, nonrelativistic formulas are
used once the kinetic energies are com­
puted.] A b o, to justify using the above
relation between σι and 0 2 , verify that the
total energies in theC-frame are comparable.
9.28 Using the law of conservation of an­
gular momentum, show that, in the decay
A 0 —» ir~ -f- p +, the resultant orbital angu­
lar momentum of the products in the C-
framc must be either zero (s-channel) or I
(p-channel). As a result, it can be shown
that the angular distribution of the pions
is proportional to I k cos φ, where φ is
the angle between the direction of motion
of the pion (in the C-frame) and the spin
of the A°-particle. Verify that this angular
distribution is incompatible with the con­
servation of parity. The experimental
value of k is 0.62. [H in t: T o prove the last
part, make a reflection in a plane perpen­
dicular to the spin of the A 0-Iiarticle.]
9.29 Show that. ij°-docay violates the con­
servation of isotopic spin. Which interac­
tion could be responsible for the process?
9.30 Let us designate the isotopic spin
wave function of a nucleon corresponding
to τ s = ± 2 by £ ( ± ) , so that £ (+ ) corre­
sponds to a proton and ξ ( —) to a neutron.
By similarity with the spin wave function
of two jiarticles (Section 4.2), write the
isotopic sjiin wave functions of two nu­
cleons corresponding to T = 0 and T = I .
In each case indicate the value of T ; .
Identify the particles involved in each
wave function.
9.31 Given that ri;· is the distance be­
tween particles i and j , show that /(r,-,-)
is translationally invariant. Determine
whether the gravitational and electric in­
teractions are translationally invariant or
not.
9.32 Make a table showing the relation
of the strong, electromagnetic, and weak
interactions to the following conservation
laws: isotopic spin, strangeness, parity,
charge conjugation, and time reversal.
9.33 IIo w are electric and magnetic fields
affected by time reversal? Show that
Problems Ί'29
M axw ell’s equations are invariant with
resjiect to time reversal.
9.33 Show that reflection 011 the X Y -
jilane (or any other coordinate jilane)
changes a right-handed frame into a left-
handed frame.
9.35 Show that if A and B are jiolar vec­
tors, then A x B is an axial vector, and
that if A is jiolar and B is axial then A X B
is jiolar. [H in t: Analyze the behavior of
A X B ujion reflection 011 the X F-planc.]
9.36 W rite the rectangular components of
L and analyze the way they change for
reflection 011 the A'l'-plane. Comjiare with
the discussion concerning Fig. 9-16.
9.37 Discuss the behavior of M axw ell’s
equations in regard to reflection 011 the
A’ F-Jilane. Do you conclude that these
equations arc comjiatiblc with conserva­
tion of parity in electromagnetic inter­
actions?
9.38 Show that a reflection at the origin
of coordinates (i.e., the change of x, y, z
into —x — y, — 2) is equivalent to a re­
flection on the A F-Jilane, followed by a
180° rotation around the A-axis. Con­
clude, then, that the jiarity behavior with
regard to reflection in a jilane and a point
are the same.
9.39 I t can be shown that, in electric
dijiole transitions, the electromagnetic
field of the jihoton has odd parity. Show
that the selection rule Al ^ 0, introduced
in Section 3.4, is required if jiarity is con­
served in the transition, or, in a more gen­
eral form, that the initial and final states
must have opposite iiarities.
9.40 Estimate the areas under the curves
shown in Fig. 9-31 and compare with the
charge of a proton and a neutron.
9.41 I t has been observed that 152Eu
decays by electron capture according to
152Eu -\- c~ —> 152Sm* -+- v. In turn, the
excited samarium decays by gamma emis­
sion according to 152Sm* —♦ 152Sm + 7.
Both 152Eu and 152Sm nuclei have zero
spin. By observing the 7-rays emitted in
<M0 Fundamental particles

a direction opposite to that of emission of

the neutrinos, physicists found that the
photons are predominantly right-handed
polarized (that is, they have negative
helicity). Show that this implies that the
neutrino also has negative helicity. [H int:
Analyze the conservation of angular mo­
mentum for the overall process.]
9.42 In the process

τ " - f p + — A0 + K 0, predominantly as shown in the figure. Is

the A ° ’s are strongly polarized, with their
spins perpendicular to the plane of produc­
tion in the direction of the vector p r X p\
(see Fig. 9-37). Is parity conserved in the
process? In the subsequent decay of A 0
into 7t and p + , the products are emitted
parity conserved in the A°-decay process?
(Compare with Problem 9.28.)
9.43 Show that if, in the 60Co experiment.
(Fig. 9-18), the electrons were emitted
with the same intensity in the forward and
backward directions, parity would be con­
served in the process.
 PART 2
STA TISTICA L PHYSICS

10 Classical Statistical Mechanics

11 Thermodynamics
12 Thermal Properties of Gases
13 Quantum Statistics
452

In the preceding chapters o f this te x t w e have studied the fundam ental con stit­
uents o f m atter: particles, nuclei, atoms, and molecules. B u t we cannot see or
feel individual atoms or molecules at work. R a th er we observe the result o f a
large number o f them actin g in a more or less organized manner; i.e., m acroscopic
processes. T h e properties o f m atter in bulk (called m acroscopic properties), as we
ord inarily observe them , are the result o f these collective actions. T h e collective
behavior of large numbers o f atom s and molecules is basically a result o f their
electrom agnetic interaction, since gravitation al interaction plays on ly a m inor
role and the strong and weak interactions affect on ly nuclear processes. Fam iliar
processes, such as m elting and vaporization, diffusion, therm al and electrical con­
duction, emission o f electrons b y hot metals, and m any others, as w ell as such
concepts as tem perature, heat capacity, heat, o f change o f phase, etc., fall in this
category o f collective properties. I t is the understanding and control o f these
collective phenomena th a t prim arily interest the applied physicist, the engineer,
the chemist, and other scientists in their endeavor to use th e forces o f nature for
the w elfare o f man.
T o describe processes in v o lvin g a v e ry large number o f particles, special m ethods
m ust be devised. T hese m ethods are, by necessity, o f a statistical nature, since
we cannot take the detailed m otion o f individual particles into account (n o r is it
necessary to make such an effo rt to obtain results o f practical valu e). F o r this
reason the discussion o f macroscopic processes from the m olecular point o f v ie w
constitutes w h at is called statistical physics. T h e w ord “sta tistica l” m ust be inter­
preted as ap p lyin g to a technique fo r describing processes in vo lvin g large numbers
o f particles whose individual interactions are known, w ith out considering the in­
dividu al b ehavior o f each particle. In this respect, statistical m ethods have been
applied to the discussion of m any-electron atom s and m any-nucleon nuclei.
In this part o f the text we shall first develop the statistical m ethod known as
classical statistical mechanics, discuss its general applications to w h at is called
thermodynamics, and apply the m ethod to analyze the properties o f gases. W e
shall conclude this part w ith a b rief introduction to quantum statistical mechanics,
illustrating som e o f its applications.
 10

CLASSICAL STATISTICAL
MECHANICS

10.1 Introduction
10.2 Statistical E q u ilib riu m
10.3 The M axicell-Boltzm ann D istribution Law
10Λ Temperature
10.5 Therm al E qu ilib riu m
10.6 A p p lica tion to the Ideal Gas
U3U Classical statistical mechanics (10.2

IO. I Introtliu-Iion
M echanics is founded on certain general principles, such as the conservation o f
energy and m omentum, that are applicable to the m otion o f interacting particles.
In this chapter we shall extend the principles o f mechanics to system s o f m any
particles, em phasizing the m ethods used to obtain collective or m acroscopic p rop ­
erties o f the system, w ith out considering the detailed m otion o f each particle. T h is
technique is called statistical mechanics. W f use “ p a rtic le" here in a broad sense,
m eaning a fundam ental particle, such as an electron, or an aggregate o f funda­
m ental particles, such as an atom or molecule. T h u s a “ p article” w ill be each of
the well-defined and stable units com posing a given physical system.
T h e fact th at we need a statistical approach when w e are dealing w ith the
macroscopic properties o f m atter is easily recognized when we note th at in one
cubic centim eter o f a gas at S T P there are about 3 X IO 19 molecules. I t is not
only practically impossible, but also unnecessary to take into account the m otions
o f each o f these molecules in detail to determ ine the bulk properties o f the gas,
such as its pressure or tem perature. On the other hand, to m ake a statistical
analysis o f a m any-particle system , we have to m ake some reasonable estim ate
about the d yn am ical state o f each particle based on the general properties o f the
particles. W e m ake this estim ate by introducing the concept o f the probability o f
distribution o f the particles am ong the different dynam ical states in which th ey
m ay be found. W h en we introduce the idea o f p robability, this does not im ply
th at we assume th at the particles m ove random ly or in a chaotic w ay, w ith ou t
obeying an y well-defined laws. T h e concept o f prob ab ility arises from our m ethod
o f estim ating the dynam ical states o f the particles in a system, not from the
mechanism b y which, as a result o f th eir interactions, the particles o f a system
are distributed in nature am ong the possible dynam ical states. H ence the v a lid ity
o f the statistical analysis o f a m any-particle system is d irectly related to the v a ­
lid ity o f our assumptions concerning the prob ab ility distribution o f the particles.

10.2 StatiHtical E q u ilib riu m

Consider an isolated system com posed o f a large number N o f particles, in which
each particle has availab le to it several states w ith energies E 1, E 2, E 3, . . . T h e
energy states m ay be quantized (as are the rotational and vib ration al states in a
m olecule) or th ey m a y form a practically continuous spectrum (as fo r the trans­
lational kinetic energy o f the molecules in a gas). A t a particular tim e the par­
ticles are distributed am ong the d ifferent states, so th at Jt1 particles have energy
E i ; V 2 particles have energy E 2-, and so on. T h e total number o f particles is

N — « i + n 2 + n 3 -T · · · = n ,·, ( 10. 1)

and w e assume th at it remains constant for all processes occurring in the system.
T h e total energy o f the system is

U — U 1E 1 + Ti2E 2 + n 3E 3 -f- · · · = ^ U iE ,·. ( 10.2 )

/0.2) Slatislical equilibrium 435

T h is expression for the total energy o f the system im p licitly assumes th at the
particles arc noninteracting (o r that they interact on ly s lig h tly ), so th at to each
particle w e can attribu te an energy depending on ly on the coordinates o f the
particle. I f w e consider interactions, we must add to E q. (10.2) term s o f the form
E Pi 2 + E p \3 + · · ■ + E p23 + · · · corresponding to the potential energy o f inter­
action between pairs o f particles. Each term includes the coordinates o f both
interacting particles. In such a case w e cannot speak o f the energy o f each particle,
but on ly o f the system.
I t m ay seem at first sight th at our discussion is therefore unrealistic, since all
particles that m ake up physical system s are interacting. H ow ever, under special
conditions w e can use a technique called the self-consistent field, in which each
particle is considered subject to the averaije interaction o f the others, w ith an
average poten tial energy which depends on ly on its coordinates, so th at w e can
still w rite U as in E q. (10.2), but now E i — E ^ 1 + E pl- ave. F o r cases in which
the interactions am ong the particles must be considered exp licitly, other tech­
niques m ust be used. W e shall discuss these in C hap ter 12 in connection with
real gases.
I f the system is isolated, the total energy U m ust be constant. H ow ever, as a
result o f their m utual interactions and collisions, the distribution o f the particles
am ong the available energy states m ay be changing. F o r exam ple, in a gas a fast
m olecule m ay collide w ith a slow one; a fter the collision the fast m olecule m ay
have slowed down and the slow one m ay have sped up. O r an excited atom m ay
collide inelastically w ith another atom , w ith a transfer o f its excitation energy into
kinetic energy of both atoms. Hence, in both exam ples, the particles after the
collision are in different states. In other words, the numbers W1, n 2, n 3, . . . , which
g iv e the partition (o r distribution) o f the N particles am ong the availab le energy
states, m ay be changing. I t is reasonable to assume th a t fo r each m acroscopic
state o f a system o f particles there is a partition which is m ore favored than an y
other. In other words, we m ay say that, given the physical cotiditions o f the system
o f particles (th a t is, the number o f particles, the total energy, and the structure
o f each p article), there is a most probable partition. W h en this partition is achieved,
the system is said to be in statistical equilibrium .
A system in statistical equilibrium w ill not depart from the m ost probable par­
tition (excep t for statistical fluctuations) unless it is disturbed by an external
action. B y this w e mean th at the partition numbers n i, n2, n 3, . . . m ay fluctuate
around the values corresponding to the m ost probable p artition w ith out no­
ticeable (o r observable) macroscopic effects. F o r exam ple, suppose th at we h a ve a
gas in statistical equilibrium , in which a m olecule o f energy E 1- collides w ith a
m olecule o f en ergy E j ; a fte r the collisions th eir energies are E r and E s. W e m ay
assume th at within a short tim e another pair o f molecules is rem oved from energy
states E r and E s and the same or another pair o f molecules is m oved into energy
states E i and E j, so th at, statistically, the p artition has not changed.
T h e key problem o f statistical mechanics is to find the m ost probable partition
(o r distribution law ) o f an isolated system, given its com position. Once the most
probable partition has been found, the next problem is to devise m ethods for de­
436 Classical statistical mechanics {10.3

rivin g the m acroscopically observed properties from it. T o obtain the distribution
law, certain assumptions are required. One m ay try several plausible assumptions,
until a distribution law in accordance w ith experim ental results is obtained.
T h re e distribution laws or statistics are presently used. One is called the M a xiu ell-
Boltzmann d istribution law, which is th e basis o f classical statistics. W e shall study
it in this chapter.
Classical statistical mechanics was developed in the last p art o f the nineteenth
century and the beginning o f the tw entieth century as the result o f the w ork of
L u d w ig B oltzm an n (1844-1906), James C. M a x w e ll (1831-1879), and Josiah W .
G ibbs (1839-1903). Classical statistical mechanics has a v e ry broad applicab ility,
especially to the discussion o f m any properties o f gases. T h e rem aining tw o dis­
tribution laws, called F e n n i-D ira c and B ose-Einstein, belong to quantum statistics
and w ill be considered in C hapter 13. Classical statistical mechanics can be con­
sidered as a lim itin g value o f the tw o quantum statistics (see Section 13.9).

I O..'I T h e X ia x irelI-IIo Ilzm a n n IHtiIrihution L a w

L e t us consider a system composed o f a large number of identical and distinguishable
particles. B y identical particles, we mean th at the particles have the same struc­
ture and com position. B jr distinguishable particles, w e mean th at we can dis­
tinguish, or tell the difference, between one particle and another identical particle.
A t first sight it seems that there is a con tradiction between identical and distin­
guishable, and indeed this is the case! L a te r on w e shall reconsider this apparent
lack o f logic; however, the results w e shall obtain now are sufficiently sim ple to
ju stify a prelim inary discussion o f such a system.

E0-------------- · -------- · --------------- «6=2

■n5=4

E4------------------- · H4= I

E11---------------· -------- · «3 = 2
F ig. 10-1. Distribution of particles V I
among different energy states.
E2 «2 = 0

EI— ·· · « I —3
-

L e t us represent a particular partition n lt η 2, n 3, . . . b y the geom etrical arrange­

m ent shown in Fig. 10-1. Each line represents a particular state o f energy JJ1, and
the number o f dots indicates the number «,· o f particles in each energy state. In
our exam ple = 3, n 2 = 0, n 3 = 2, n4 = I, etc.
Our first assumption is th at all energy states are equally accessible to the par­
ticles o f the system ; i.e., that all energy states have the same probability o f being
i0.3) The Maxwell-Bollzmann distribution law 437

occupied. T h e n we shall assume that

the probability o f a particular pa rtition is proportional to the number o f

different ways in which the particles can be distributed among the avail­
able energy states to produce the partition.

L e t us then see, as an exam ple, the number o f different ways in which the partition
o f Fig. 10-1 can be obtained. B y differen t we mean th at the numbers Ji1, n 2, n 3, . . .
are fixed, but the particles in each state are different. T h a t is, a partition in which
particle a is in state E i and particle p is in state E 3 is considered different from a
partition in which particle a is in state E 3 and particle p is in state E t . T h is is a
consequence o f assuming th a t the com ponent particles are distinguishable. If
they were indistinguishable, we would have to assume th at the tw o partitions
were the same.
T o start fillin g the state E 1, we m ay select the first particle from any one o f the
N particles available. T h e n there are N distinguishable ways o f selecting the first
particle. T h e second particle can be selected in JV — I different ways, since on ly
N — I particles are left available. A n d the third particle can be selected in N — 2
different ways. So the total number o f different distinguishable w ays in which we
m ay select the first three particles to place in state E 1 is

f N (N - I)(A T - 2) = -( f r ' (10-3)

L e t us designate the three chosen particles b y a, 6, and c. W e m ay pick them in

any o f the 31 = 6 different orders or perm utations abc, bca, cab, bac, acb, cba.
B u t these 3! different orders o f placing particles a. b, and c in E i g iv e the same
partition, since they all correspond to particles a, b, and c, in state E i . A partition
is determ ined on ly by the number and labeling o f particles in each state and not
b y the order in which they w ere placed there, which is im m aterial once the p arti­
tion is arranged. T herefore, to obtain the total number o f distinguishable d ifferent
w ays in which we m ay select the first three particles in state E u w e must d ivid e
E q. (10.3) by 31, resulting in

N\
3 !( jV - 3 )!

T h e general expression fo r the total number o f distinguishable different w ays o f

placing η i particles in state E i Ls then

ΛΠ
' V· (10.4)
Ji1 IO V - Ji1) !

T h is i s just the number o f perm utations of N objects, taken J i 1 a t a time. W hen we

pass to the second state E 3, on ly N — j? j particles are available. So if w e want to
place Ji2 particles in state E 2, we must use E q. ( 1 0 . 4 ) with N replaced by N — J i 1
038 Classical statistical mechanics (10.3

and Wi replaced b y W2, resulting in

( N — W i)!
(10.5)
n 2\ (N — Wi — n o )!

F o r the third state w e have on ly N - I i i - n 2 particles left, and we are placing

w3 particles in it, so th at instead o f Ecp (10.4) w e g et

(N - T i 1 - w2) l
w 3l ( i V - T i 1 - n 2 — W3) !

T h e process can be continued until all energy states h ave been considered. The
total number o f distinguishable d ifferent w ays o f obtaining the p artition n j, n 2, n 3,
. . . is obtained b y m u ltip lyin g expressions (10.4), (10.5), and the successive ex­
pressions for all rem aining energy states. In doin g this the student m ay note th at
a number o f factors, such as ( N — W1)!, ( N - U 1 — n2) I etc., cancel out, resulting
in the sim plified expression

AT'
P = , , ' (10.6)
Wilw2Iw3! . . .

which gives th e number o f differen t distinguishable w ays in w hich the partition

Wi, w2, w3, . . . can be obtained. W e shall now assume th at the p rob a b ility of
obtaining th at partition is proportional to P . F o r exam ple, for the partition o f
F ig. 10-1, the prob ab ility P is

NI
P =
310121114!

W e must take 0! equal to I, since w,· = 0 can be chosen in on ly one w ay. T h e

numbers W 1, w2, n 3, . . . in E q. (10.G) must be chosen in such a w a y th at Eqs. (10.1)
and (10.2), which g iv e the total number o f particles and the total energy, are
satisfied.
So far w e have assumed th at all availab le states have the same p ro b ab ility of
being occupied. I t m ay happen that the states have different in trin sic probabilities
cji.F o r exam ple, a certain energy state m ay be com patible w ith more differen t
angular m om entum states than other states, and therefore is m ore lik ely to be
occupied. W h en this intrinsic p rob ab ility is taken into account, the p rob ab ility
P o f a g iven partition is sligh tly d ifferent from E q. (10.6). O bviously, if </, is the
p rob ab ility o f finding a particle in the le v el o f energy E il the prob ab ility o f finding
tw o particles in th at level is <7,· X <7, = y f, and for n, particles it is <7,· X g,- X g, X
• · ■ X (Ji = <7?·· Thus the total p rob ab ility o f a g iven partition, instead o f being
g iven b y E q. (10.6), is given by
10.3) The Maxwell-Rollzmann distribution law 439

F in ally let us rem ove the condition o f distinguishability. I f all particles are
identical and indistinguishable, one cannot recognize the difference if, fo r example,
in the p artition in Fig. 10-1 particles a and p exchange places. T h erefo re all N !
perm utations am ong the particles occupying the different states g iv e the same
partition. T h a t means th at w e have to d iv id e E q. (10.7) by N !, resulting in

nI JV it :
I1 = g l g 2 -g-3 - - = Π - y (10.8)
n i\ n 2\n3\ . . . “ «,·!

Th is is the expression for the p rob ab ility o f a distribution in M axw ell-B oltzm an n
statistics.
W e can obtain the equilibrium state, corresponding to the m ost probable par­
tition, b y finding the m axim um o f P (given by E q. 10.8) com patible w ith condi­
tions (10.1) and (10.2), w ith N and U as constants. T h e m ethod is a straigh t­
forw ard m athem atical technique, and is explained in detail in E xam ple 10.1. T h e
result is th at the partition h a vin g maxim um p rob ab ility is given by

η, = (10.9)

where a and β are tw o param eters which,asw ill be shown,are related to the
physical properties o f the system . T h e qu an tity a m ay be expressed interm s o f
the total number o f particles, N . U sing Eq. (10.9), we have that

N = « I 4- n 2 + « 3 + · · ·

= + ■· ·
= e ~ a((jie ~ at:> + (j2e~i>E* - f <]3ε ~ βΕ* -j )

= e “ ( Σ (J , C - s k ^ = C r a- Z t

where

Ζ = Σ ο > ϋ- βΕί. (10.10)

T h e qu a n tity Z , called the partition fun ction , is a v e ry im portant expression which

appears qu ite often in m any calculations. W e m ay thus w rite e ~ a — N /Z, and
Eq. (10.9) becomes

». = (10.11)

Expression (10.11) constitutes the M axicell-Boltzm ann distribution law. T h e quan­

tity β is related ,to the en ergy o f the system , or m ore precisely, to the average
energy o f a particle, as w ill be explained in Section 10.4.
W e shall now illustrate an application o f E q . (10.11). From the definition o f
average value, w e h a ve that the avera ge value (fo r a g ive n p artition ) o f a physical
 ■I mechanics {10.3

expressed as a function of the particle energy E is given

L* J
.e m ost probable or equilibrium partition we have, using E q. (10.11),

E avc = \Σ m n E i l e - * * '. ( 10. 12)

F o r exam ple, if the particles o f a system can be in on ly tw o states o f energy,

EI = + « and E 2 = — e, both w ith the same prob ab ility (I jl = g2 = I ) , then

Z = e~^E' + e~^E2 = e_i3‘ + eP' = 2 cosh β (,

and the average energy o f a particle is

T h e total energy is

U = N E livc = — N e tanh /3e,

which allows us to find /3 in term s o f U .

E X A M P L E 10.1. Derivation of the most probable or equilibrium partition.

S o lu tio n : The most probable or equilibrium partition corresponds (by definition) to

the maximum of P . This maximum, in turn, corresponds to the situation in which the
change of P is practically zero (d P = 0) for small changes dm, dm, dm, . . . in the occu­
pation numbers m , « 2, « 2, ■ ■ ■ However, instead of obtaining the maximum of P , it is
easier mathematically to obtain the maximum of In P , which corresponds to the same
value of P . Now, from Eq. (10.9), we have

In P = m In 3 i -+- m In g2 + «3 In gs + ■· ·
— In m ! — In na! — In ηβ! —

Using Stirling’s formula for the logarithm of the factorial of a very large number (see
Appendix V ),

In x! «= x In x — x,

and assuming that m , m , m , · · · are large numbers (since physical systems are in gen­
eral composed of a great many particles), we have

In P = m In gi + m In g2 -f- m In 33 + · · ■
— (m In m — m ) — (m In m — n2) — (m In m — « 3) —
= — m In m /si — m In n i/ g i — · — f- (m + n2 ---- ·),
10.3) The MaxuieU-Bollzmann distribution law V tl

or, using Eq. (10.1), we may write

In P = N — ^ Hi In UiZgi. (10.13)

Differentiating this expression (remembering that N is constant and thus dX = 0),

we obtain
d(ln P ) = — (dm ) In HiZgi — ^ i n ‘ ^ ln »*/?.)

(10.14)

But from Eq. (10.1), since d X = 0 because N is constant, we have

(10.15)

Therefore Eq. (10.14) reduces to

(10.16)

We write zero on the right side of Eq. (10.16) because we are looking for the equilibrium
state for which P is maximum, or d P = 0, and therefore d(ln P ) = P ~ 1 d P = 0. If all
the changes dm, d m , dn-j, . . . were arbitrary, we could satisfy Eq. (10.16) by making

In n i/gi = 0, In mZg-z = 0, In n-s/gs = 0, . . . or m = Si, m = 92, · ■ ·

However, the changes dn, are not entirely arbitrary because of condition (10.15), which
was derived from the constancy in the number of particles, and a similar condition,

(10.17)

resulting from the constancy of the internal energy and obtained by differentiating
Eq. (10.2) and setting d U = 0.
T o compensate for the two conditions (10.15) and (10.17), we introduce two arbitrary
parameters a and 0, called undetermined multipliers, according to a mathematical tech­
nique suggested by Lagrange (see Appendix V I I ). Multiplying Eq. (10.15) by a,
Eq. (10.17) by β, and adding these to Eq. (10.16), we obtain

T . (In n j g i + a + β Ε ί) dm = 0.

This adds two new arbitrary coefficients a and β to compensate for the two restrictive
conditions (10.15) and (10.17). The equilibrium distribution is then obtained if

In UiZgi + a + β E i = 0
or
m = g te --* *

which is the result previously stated in Eq. (10.9).

 I

U i Classical statistical mechanics ( 10.3

E X A M P L E 10.2. A system is composed of 4000 particles which may be in one of three

energy states or levels, equally spaced, whose energies arc 0, c, and 2e, all having the same
intrinsic probability g (see Fig. 10-2). This system, for example, could consist of atoms
whose total angular momentum is equal to I , placed in a magnetic field. Compare the
relative probabilities of the partition in which there are 2000 particles in the lower level,
1700 in the middle level, and 300 in the upper level with the partition resulting from the
transfer of one particle from the middle level to the lower level and another to the upper
level, a process compatible with the conservation of energy.

E3=Q i----------------------------------------- «3

E3=I -----------------------------------------
F ig. 10-2. System with three
energy levels. ^ _ 0 -----------------------------------------„ ,

S o lu tio n : According to Eq. (10.8), the probabilities for the first and second partitions arc

4000 4000

Pr = — — f - — — P 2 = ----- 9 ------------
2000117001300! ‘ 20011109813011

Instead of computing the values of P\ and P 2 (which we could do by using Eq. 10.13),
we shall simply find their ratios:

P2 1700 X 1699 2,888,300

Pi ~ 2001 X 301 ” 602,301 “ ' '

Thus the mere transfer of two particles out of 4000 to other levels changes the probability
by a factor of 4.8. This means that partitions P i and P 2 are both far from being the
equilibrium partition; this situation is due to an excessive population of the middle level.
Therefore the system will try to evolve to a state in which the middle level is less popu­
lated. I t is suggested that the student repeat the problem, considering other possible
distributions of particles, all compatible with the same total energy. (Shift two more
particles from the middle level or move one particle from the upper level and another
from the lower level into the middle level and recompute the relative probabilities.)

E X A M P L E 10.3. Determine the most probable or equilibrium partition for the system
of Example 10.2.

S o lu tio n : The system is composed of N = 4000 particles, and according to the data
given in Example 10.2, its total energy (see Fig. 10-2) is 2000 X O f 1700 X i - f 300 X
(2e) = 2300c. Using Eq. (10.9) for the most probable partition, we must have, according
to the notation of Fig. 10-2, and with gi = g2 = g2 = g,

n I = gc~a, H2 = ge~a~ie, n2 = ge~“ ~ 2i,i

or, if we designate e~s' by x, we have n2 = n ix and rag = m x 2. Thus conditions (10.1)

and (10.2), which give the total number of particles and the total energy, respectively,
become
« 1 + n i z + n\x2 = 4000, (m :r)c-j- ( m i 2)(2c) = 2300c.
ίΟ Λ) Temperature hti3

Canceling the common factor t in the second relation, we have

m (l + X + X 2) = 4000,
m ( x + 2x2) = 2300.

Eliminating n\, we obtain an equation for x:

47x2 + 17x - 23 = 0,

or x = 0.5034. (Only the positive root is used. W hy?) T h ereforeni = 2277 (the figure
has been rounded). Accordingly, «2 = 1146 and 713 - 577. Thecorrcspondingpartition
probability is
4000
9___
2277111461577!

L e t us now compute the change in P when two particles are removed from the inter­
mediate level and transferred to the upper and lower levels. The new partition prob-
ability- is
4000
pt tj__________
2278111441578!

The ratio of the two probabilities is

P' 1146 X 1145 1,312,170 „„„„„

— = = — = 0 0066
P 2278 X 578 1,316,684

Therefore the two probabilities are essentially the same; this is as it should be, since, if
P is a maximum, A P must be zero or very small for a small change in the distribution
numbers of an equilibrium partition.

10.4 T v m p v ra iu rv
T h e param eter β o f Eqs. (10.10) and ( 10.11) is d irectly related to a physical quan­
tity , the tem perature, which was originally introduced m ore to describe a sen­
sorial experience than a statistical property o f an aggregate of particles. W e first
note th at, if we are to have dimensional consistency in Eqs. (10.10) and ( 10.11),
we m ust express β in reciprocal energy units; th at is, J - 1 , e V - 1 , etc. Using
E q. ( 10. 11), we have that the total energy o f a system o f particles in statistical
equilibrium is

U — TI1E 1 + TI2E2 + n^Es + · · ·

= f (giEie-**' + g^E#-*** + g3E3e~fiEi + · · ·)

or

( 10. 18)
Wi Classical statistical mechanics

Using the d efin ition (10.10) o f the partition function, we m ay w rite U in the
altern ative form

u ~ ~ I - - 1 1 - Th m - <l 0 l 9 >

which is an im portant relation between the total energy and the partition function
o f a system in statistical equilibrium . T h e average energy o f a particle is

E ave = ft
^ = J j(In Z ). ( 10.20)

N o te that, given a physical system described b y the g/s and the Ε Ϊ s, the partition
function Z (and hence the total energy U ) as well as the average energy o f a par­
ticle, LiJavei are functions o f β (and also other param eters which determ ine the
m acroscopic state, such as volum e and pressure). T h a t is, we m ay use the param ­
eter β to characterize the internal energy o f the system. H ow ever, it has been
found more convenient to introduce a new physical q u a n tity instead o f β. T h is
qu an tity is called the absolute temperature o f the system ; it is designated by T , and
defined according to the relation

fc r = i · (10.21)

T h e q u a n tity k T must obviously be expressed in units o f energy, such as joules

or electron volts. T h e constant k is called the LiolUmann constant. Its value is
determ ined after the units for T are chosen. It remains to be shown th at the
tem perature we have defined here coincides w ith the tem perature as measured by,
say, a gas therm om eter. W e shall do this later on (Section 12.2). A t this tim e it
is enough to say that when T is expressed in a unit called degrees kelvin, designated
b y 0K (w hich was introduced before statistical mechanics was d evelo p ed ), the
value o f the B oltzm ann constant is

F = 1.3805 X IO- 2 3 J 0K -1 = 8.6178 X 10- 5 e V oK - 1 .

O f course, we could m ake k = I and measure the tem perature d irectly in energy
units, such as joules or electron volts. T h is is p erfectly possible. H ow ever, the
tradition o f expressing tem perature in degrees, introduced lon g before the relation
between tem perature and the m olecular structure o f a system was recognized, is
so well entrenched in physics that it is alm ost im possible (and perhaps also unde­
sirable) to do aw ay w ith the use o f degrees. T h e qu a n tity β is p ositive (except in
some special cases), as w ill be shown later; hence the absolute tem perature T is
positive. T h e low est tem perature is zero, which corresponds to w h at is called
absolute zero.
I t must be clearly kept in m ind th a t the statistical definition o f tem perature, as
given b y E q. (10.21), is valid only fo r a system o f particles in statistical equilib­
rium, and hence does not ap p ly to a single particle or to a system which is not in
iOA) Temperature Ithp

equilibrium . T h e reason fo r this is that the param eter β appears on ly in connection

w ith the calculation o f the m ost probable p artition o f a system, which corresponds,
b y definition, to the equilibrium state. I f the system is not in equilibrium , w e
m ay still speak o f an “e ffe c tiv e ” tem perature o f each small portion o f the system,
assuming th at each small portion is almost in equilibrium .
W h en w e introduce the d efin ition (10.21) o f tem perature in E q. (10.10), we
m ay w rite the equilibrium partition function as

Z = Σ 9‘e~ BilkT· (10.22)

*

Sim ilarly, the equilibrium occupation numbers are given by

Ui = j g i e ~ EilkT, (10.23)

which gives the M axw ell-B oltzm an n distribution law in terms o f the tem perature.
Since β = 1/kT, then άβ = — d T / k T 2, and we can w rite E q. (10.19) as

U = kN T2 ~ (In Z ). (10.24)

T h e average energy per particle, U / N 1 is given b y

E ivc = kT2 (In Z ) . (10.25)

N o te th at E q . (10.25) establishes a relation between the average energy per par­

ticle o f a system in statistical equilibrium and the tem perature o f the system .
T h e exact relation ob viou sly depends on the m icroscopic structure o f the system,
which is expressed in the partition function Z 1 and is different for an ideal gas, a
real gas, a liquid, or a solid. H ence we m ay say th at the temperature o f a system
in statistical equ ilib riu m is a quantity related to the averaye energy per particle o f the
system, the relation depending on the structure o f the system.
In the general case, the average value o f an y particle property, F ( E ) , which
was defined in E q . (10.12), now becomes

E nvc = 9 i F ( E i ) e - BilkT, (10.26)

I

and is thus a function o f the tem perature. F o r exam ple, for the system composed
o f particles o f energies -f-e and — e, considered at the end of Section 10.3, the aver­
age energy o f a particle at the tem perature T is

Eavc = * -e tanh (e / k T ).

Since the exponential e ~ E‘:kT in Eq. (10.23) is a decreasing function of E J k T 1

the larger the ratio E J k T , the sm aller the value o f the occupation number n,·.
T h erefore, at a g ive n tem perature, the larger the energy E 11 the sm aller the value
M6 Classical statistical mechanics

o f n,·. In other words, 'the occupation o f states a vailab le to the particles decreases
as th eir energy increases. A t v e ry low tem peratures on ly the low est energy levels
are occupied, as shown in F ig. 10-3; but at higher tem peratures (corresponding to
sm aller values o f E i/ k T fo r a given en ergy) the rela tive population o f the higher
energy levels increases (again as shown in F ig. 10-3) by transfer o f particles from
low er to higher energy levels. A t the absolute zero o f tem perature, on ly the ground
or low est energy level is occupied. N o te th a t the relation of the occupation num­
bers between tw o energy levels E , and E j is

_ OJ - ( B i - E i) I k r _ 0± -B B lk T
Ti.· gi Oi
(10.27)

where A E is the energy difference be­

tween the tw o levels. Thus «,· and n j are
com parable o n ly if A E is much sm aller
than k T .

F ig. 10-3. Maxwell-Boltzmann distribu­

tion at three different temperatures.

E X A M P L E 10.4. Giv0n temperatures of IOO0K 1 300°K (room temperature), and

IOOO0K , determine for each temperature the ratio between the occupation numbers for
two levels corresponding to A E equal to: (a) IO-4 eV, which is a value equivalent to the
spacing of rotational levels for many molecules, (b ) 5 X IO-2 eV, which corresponds to
molecular vibrational levels, and (c) 3.00 eV, which is of the order of magnitude of elec­
tronic excitation of atoms and molecules. Assume 9 = 1.

S o lu tio n : Remembering that k = 8.6178 X IO-5 cV 0K -1 , we have that A T = 8 .6I78X

IO-5 T e V , and A E /kT = 1.1603 X 10* A E / T , where A E is expressed in electron volts.
Therefore, for the indicated values of AE, the values of η,/η, at the three temperatures
are as given in the following table.

AE, eV IOO0K 300°K IOOO0K

IO-4 0.9885 0.9962 0.9988

5 X IO-2 3 X IO-3 1.45 X IO-1 5.60 X IO-1
3.00 3 X IO-104 8 X IO-49 8 X 10-1G

Therefore, for A E = IO-4 cV, the two levels are practically equally populated at all
temperatures considered. This explains, for example, why' the complete rotational ab­
 Temperature Mt7

sorption spectrum of molecules is observed at normal temperature, as illustrated in

Fig. 5-35 for HCl. A t A A’ = 5 X IO-2 eV, the population of the upper level is already
appreciable at room temperature, which means that many molecules are in an excited
vibrational state at room temperatures. However, for ΔΛ' = 3 e V , the ratio η,/η, is so
small that it is plausible to consider the upper level as essentially empty at all tempera­
tures considered. Thus most atoms and molecules (at room temperature) are in their
ground electronic state. Only at extremely high temperatures, as in very hot stars, are
there atoms and molecules In excited electronic states in any appreciable amount. In
the laboratory, electronic excitations are produced by means of inelastic collisions of
gas molecules with fast electrons in an electric discharge.

E X A M P L E lO.ii. Consider a system of polar molecules which are placed in a uniform

electric field, but which arc otherwise isolated from any other external action. Compute
the polarization of the system as a function of the temperature.

S o lu tio n : Let us designate the electric dipole moment of each molecule by po- We
shall assume that the effect of the applied electric field is only to modify the random
orientation of the molecules without disturbing their translational or internal (rotational
or vibrational) motions, and that the molecules are free to follow the orienting action of
the electric field. The energy of a molecule whose dipole moment makes an angle Θ with
the electric field £ is E(O) = — ροδ cos Θ. Since the angle Θ can have any value between
0 and x, the energies of the available states are not discrete but vary continuously. Thus,
instead of looking for the number of molecules oriented at an angle 0, we must find the
number of molecules with their dipoles oriented within the solid angle dll, defined as
being between cones of angles 0 and Θ -f- dO (Fig. 10-4). The value of this solid angle is
dll - 2x sin Θ <10, and using Eq. (10.22) with <y, replaced by r/Ω and the summation re­
placed by an integral, we may write the partition function as

Z = Γ Cpoecos9m7^ x sin Odd = 4x(fcT/p06) sinh (ροδ/JfcT).

Jo

The orientation of the molecules must be symmetric relative to the direction of the elec­
tric field and the average value of their electric dipole moment is parallel to S. Thus, to
find pav<„ we must evaluate (po cos 0)aVc, since po cos 0 is the component of the electric
dipole moment in the direction of δ. Using
Eq. (10.26), with the summation replaced
by an integral, we have

Pavc — ^ [ (Pa COS 0)e’’oE“ s,/M'2r sin Θ dO

Z Jo

( .. ροδ kT\
= P O ^ c o th -- — j,

a result which is called Langevin’s formula. A t very large δ or very small temperature
(that is, for ρ ο δ » k T ), we have that coth ( poK/kT) —> I and kT/poE —» 0, so that
Pavc = Po· This means that for a very large electric field, or at temperatures near abso­
lute zero, practically all molecules are oriented parallel to the electric field. For small δ
IM Classical statistical mechanics (/0.5

or large T (that is, p»?,/kT « I), we use the asymptotic expansion

coth x = M x -Y x/3 -J- · · · ,

and thus
/ W = p lt/ Zk T .

If there are n molecules per unit volume, the polarization of the substance is

(P = J ip avc = (npo/3kT)Z.

This expression is used in the calculation of the electric perm ittivity of a medium com­
posed of polar molecules. The magnetization of a substance placed in an external mag­
netic field when the molecules have a permanent magnetic moment is obtained by a
similar calculation. This is the orientation effect which gives rise to paramagnetism. In
this case, however, a complication arises. The magnetic moment is related to the angular
momentum, which is restricted in orientation, as indicated in Section 3.4. Thus instead
of performing an integration, we must perform a summation. The final result is still
very similar to that obtained for an electric dipole moment (see Problem 10.8).

10.5 T h v rm a l Iiqnilihrium
Consider a system com posed o f tw o differen t groups o f particles. W e shall say th at
each group o f particles constitutes a subsystem. Our tw o subsystems m ay, for
exam ple, consist o f a liquid w ith a solid im mersed in it, a m ixture o f tw o gases or
liquids, o r tw o solids in contact. B y means o f collisions and other interactions,
energy m ay be exchanged between the particles com posing the tw o subsystems,
but the total energy o f the whole system is assumed to be fixed. L e t us designate
the total numbers o f particles in each subsystem b y N and iV'and the correspond­
ing energy levels availab le to the particles by E j, E 2,Eri, . . . and E E 1
2, E 2, . . .
I f there are no reactions between the particles in the tw o subsystems, the total
number o f particles in each subsystem is constant; also the to ta l energy o f the sys­
tem is constant. B u t the en ergy o f each subsystem is not conserved because, due
to th eir interactions, energy m ay be exchanged between them. T h erefo re the fo l­
low ing conditions for the tw o subsystems must be fulfilled by the occupation num­
bers « I , η ,, Ji3, . . . , and n\, n'2, Ji3, . . . in a given partition:

N — y ; Ji1- = const, (10.28)

i

NJ = Y 1 nJ ~ const, (10.29)
j

U = Y j UiE i + Y n 'jE j = const. (10.30)

' i '
T h e p rob ab ility o f a g iven partition or distribution is g iven by the product o f tw o
expressions sim ilar to E q. (10.8), one for each subsystem :

gVgFg? V inV 2nV 3"* · · -I (10.31)

P = X
H1!Ji2IJial - n\ In1
2In3 1 . . . -I
 I
Thermal equilibrium 669

W c can obtain the equilibrium o f the com posite system b y requiring th a t P be a

maximum, com patible w ith Eqs. (10.28), (10.29), and (10.30). T h e result (see
E xam ple 10.0) is th at

Mi = f g n T 9**, n'j = ~ Iή β - βΕΚ (10.32)

where Z and Z ' arc the respective partition functions o f the tw o subsystems. We
also note th at the tw o subsystems in equilibrium must have the same param eter β.
In v ie w o f our definition o f tem perature, E q. (10.21), w e conclude that

Uco different and interacting systems o f particles in statistical equilib­

riu m must have the same temperature,

a statem ent called the zeroth law o f thermodynamics. It is then said that the sub­
systems are in thermal equilibrium . H ence, when w e replace β by Ι /k T , instead of
Eq. (10.32) we m ay w rite

N e-B ilk T , W 0'e ~ E'ilkT

nI — Z 1 Zr }

where T is the com mon absolute tem perature o f the tw o subsystems. T h e expres­
sions for « , and n'j show that at therm al equilibrium each subsystem attains the
same m ost probable .partition as if it were isolated and a t the same tem perature T .
These relations therefore express the fact that, in a statistical sense, a fte r therm al
equilibrium is attained the energy o f each subsystem remains constant. T h is
means that, although both system s m ay exchange energy at the m icroscopic
level, the exchange takes place in both directions and, on the average, no net
energy is exchanged in either direction. T h erefo re, statistically, the en ergy o f each
subsystem remains constant. I t then follow s th at when tw o bodies at d ifferent
tem peratures are placed in contact th ey w ill exchange energy until both reach
therm al equilibrium at the same tem perature. A t this point no further net exchange
o f energy takes place.
T h e zeroth law is the basis o f the m easurem ent o f the tem perature o f a b o d y ;
this tem perature is determ ined by placing it in contact w ith a p roperly calibrated
standard b od y (o r therm om eter). T h e zeroth law is also in agreem ent w ith our
common understanding o f the concept o f tem perature by which, if a “c o ld ” and
a “h o t" b od y are placed in contact, the cold warm s up and the hot cools off until
both are “ f e lt ” at the same tem perature. T h erefo re, although the concept o f
tem perature was first introduced to correspond to a sensorial experience which is,
o f course, associated w ith a physical condition o f the human body, it can now be
defined precisely by means o f the statistical relation (10.21).

E X A M P L E 10.6. Derivation of relations (10.32).

S o lu tio n : When P is given by Eq. (10.31), if we follow the same procedure used to obtain
Eq. (10.16), we have

—d(ln P ) = Y j In n,/g, dm + In n'ffg', dn'j = 0. (10.33)

450 Classical statistical mechanics (10.6

The restricting conditions (10.28), (10.29),-and (10.30) now give

Y dn, = 0, (10.34)

Y dn'i = 0, (10.35)
j

Y l E i dm + J ^ E 'j d n 'j = 0. (10.36)

M ultiplying Eq. (10.34) by a, Eq. (10.35) by a', and Eq. (10.36) by β, and introducing
these in Eq. (10.33), we gel

Y (In UiZgi + a + β Ε β dn,· + Y i + a ' + βΕ )) dWj = 0,

(In Wjfg1

which requires (for the same reason as in the case of only one kind of particle) that

In TtiZgi + a + /SE; = 0, In Wjfgi + a ' + β E ri = 0.

Accortlingly we get
—a —βΕ{ / / —a*—βΕ:
Tii = giC ·, Wi = g ,c

or, using relations (10.28) and (10.29) to eliminate e- " and e~a’

N ote that we use a and a ' because the number of particles of each subsystem is conserved
separately, but we use only one β because it is the total energy which is conserved.

IO M Appliea tiu n to the Itleal lias

O ur next step is to determ ine w hether there is any system o f particles in nature
whose collective beh avior resem bles the predictions o f the M axw cll-B oltzm an n
distribution law. U p to this point w e h a ve presented this distribution on ly as a
m ore or less reasonable th eoretical construction. Experience confirms the fact
th at m ost gases can be described according to M axw ell-B oltzm an n statistics o v e r
a w id e range o f tem perature. F o r sim p licity we shall now consider ideal gases
com posed o f m onatom ic molecules. In this w a y we do n ot have to include the
poten tial energy due to the intcrm olecular forces nor the energy associated w ith
internal rotational or vib ration a l m otions o f the molecules, and all m olecular
energy is translational k inetic; th at is, E i in E q . (10.11) is

(10.37)

B u t we note, as explained in E xam ple 2.0, that the kinetic energy o f an ideal gas
occupying a rather large volum e m ay be considered as not being quantized but as
havin g a continuous spectrum. T h erefo re we m ust rew rite E q. (10.22), replacing
 Application Io the ideal gas 451

the sum by an integral in the form

Z = Γ e - ElkTg ( E ) (IE , (10.38)

Jo

where g (E ) d E replaces g, and represents the number o f m olecular states in th e

energy range between E and E + d E . T h is number arises from the d iffe re n t
orientations o f the m om entum /> for a given energy. Trom Eq. (2.30) o f E x a m ­
ple 2.6, we have that

g (E ) d E = - 7ΓΪ ( ^ 3)1/2 E v 2 d E , (10.39)

where V is the volum e occupied b y the gas. T h erefo re

z = 4 r V (2 m * )u * f -EikT dE
ft Jo

T h e integral appearing on the right can be found (see A ppendix I V ) to have th e

value A V V ( A T ) 3. T h erefo re

g = VVrmkT)" t
ft·5

which gives the partition function o f an ideal m onatom ic gas as a function o f th e

tem perature and the volum e o f the gas. Th en , by taking the natural logarithm o f
each side, we have

In Z = C + § In AT,

w here C includes all the rem aining constant quantities. Substituting this value o f
In Z in E q . (10.25), we obtain the average energy o f the m olecules as

Eavc = §AT. (10.41)

T h erefore the average kinetic energy o f the m olecules o f an ideal gas in statistical
equilibrium is proportional to the absolute tem perature o f the gas. H is to ric a lly,
Eq. (10.41) was introduced in the nineteenth century, lon g before the developm en t
of statistical mechanics, in connection w ith the kinetic th eo ry o f gases. I t was
this relation th at suggested the identification o f β w ith 1/AT. T h e total en ergy
o f a gas com posed o f V molecules is then

U = N E nvc = § A:V T .

W e conclude then that the internal energy o f an ideal m onatom ic gas depends
on ly on its tem perature. T h is is a direct result o f our definitions o f an ideal gas
and o f tem perature. W e do not expect the same relations to hold for real gases o r
other substances, since their internal energy is p artly potential and thus depends
on the separation o f the m olecules; that is, on the volum e o f the substance.
452 Classical statistical mechanics (10.6
'I n

<11·:

F ig. 10-5. Molecular energy distribu­

tion a t two temperatures (100°K and
300°K). Note, from Eq. (10.44), that the
energy distribution is independent of the
molecular mass.

3 (Χ Π <

4.(1 5.0 (i.ll 7.(1 N.O

AM Iir2 I-V)

I f N is the num ber of m oles* o f the gas, and N,\ = 6.0225 X IO2'1 m ole-1 is
A v o g a d ro ’s constant, which is the number o f m olecules in one m ole o f the sub­
stance and which is the same fo r all substances, we have n = N/N Thus

U = % N k N \ T = §N R T , (10.42)
where
R = IcN a. = 8.3143 J m ole-1 0K -1
= 1.9800 calories m ole-1 0K -1
= 5.1894 X IO 19 e V m ole-1 ° K -1 (10.43)

is called the gas constant.

Expression (10.23) for the distribution o f m olecules am ong the different energies,
w ith g, replaced by (I(N ) (IE as g ive n b y E q. (10.39), is now

, N - E l k T ,rt\ j p N 47TF(2m3) 1/2 , , 1/2 - E l k T JJ7

an = -y e y {L ·) a h = yr tt. L· c da,
Zj Z fl

where (In is the number o f molecules w ith energy betw een E and E + (IE . By
introdu cing the value o f Z as g ive n by E q . (10.40), we have

dn 2 πN - i n - E ik T Ctoin
Jm W 2 e 1 ( l 0 '44)

which is M a x w e ll’s form ula fo r the energy distribution o f the m olecules in an ideal
gas. T h is constitutes one o f the earliest applications o f statistical m ethods in
physics. I t was origin ally derived by Jam es C. M a x w ell around 1857, using a
different logic. A plot o f E q. (10.44) for tw o differen t tem peratures is represented
in Fig. 10-5.

* Recall that one mole of a substance is an amount of that substance, in grams, equal to
its molecular mass expressed in amu.
10.6) Application to the ideal gas 053

i t 1I
dr

F ig. 10-6. Molecular velocity distribu­

tion for oxygen at two temperatures (80°K
and 800°k). Note, from Eq. (10.45),
that the velocity distribution depends on
the molecular mass.

'/' = S(X)0K

(I I 8 12
v (10- m s~')

Som etim es w e require the v elocity distribution rather than the energy distribu­
tion. N o tin g that E = Jmt'2, we then have th at

civ d E dv mv ~ ~ ■
dE

M a k in g the substitution E = Jma2 in E q. (10.44), we get

(10.45)

which is M a x w e ll’s form ula for the velo c ity distribution o f the molecules in an
ideal gas. It gives the number o f molecules m ovin g with a velo c ity between v and
v + dv, irrespective o f the direction o f m otion. T h e v e lo c ity distribution for
oxygen a t tw o different tem peratures is represented in Fig. 10-0.
A crucial test o f the ap p licab ility o f M axw ell-B oltzm an n statistics to ideal
gases is to see whether the energy and v e lo c ity distributions illustrated in Figs. 10-5
and 10-6 actu ally occur. One indirect w a y o f doin g this is to an alyze the depen­
dence o f the rate o f chemical reactions on the tem perature. Suppose that a par­
ticular reaction occurs on ly if the colliding m olecules h a ve a certain energy equal
to or larger than E a. T h e rate o f reaction a t a g iven tem perature then depends on
the number o f molecules havin g an energy equal to or larger than E a. T h ese num­
bers, for tw o different tem peratures, are given b y the shaded areas under the Iow-
tem perature and high-tem perature curves o f Fig. 10-7. W e note that there are
m ore molecules available at high than a t low tem peratures. B y proper calcula­
tion, we can predict the effect o f these additional molecules, and the theoretical
prediction can be com pared w ith the experim ental data. E xperim ental results are
in excellent agreem ent with E q. (10.45); this confirms the app licab ility o f M a x w ell-
B oltzm an n statistics to gases.
454 Classical statistical mechanics (10.6
dn
dE

F ig. 10-7. Number of molecules with energy larger than E a at two different tempera­
tures. The number in each case is indicated by the shaded area.

A m ore direct verification would consist in an actual “cou n t” o f the number of

molecules in each energy or v e lo c ity interval. Several experim ental arrangem ents
have been used fo r this purpose. One m ethod, using a ve lo c ity selector or “ chopper, ”
is illustrated in Fig. 10-8. T h e tw o slotted disks, D and D ', rotate w ith an angular
velo c ity ω and th eir slots are displaced b y an angle Θ. W h en gas molecules escape
from an oven a t a certain tem perature (a process called effusion), th ey pass through
both slots and are received a t the detector on ly if their v e lo c ity is v = scj/Θ. A c tu ­
ally, since the slots have a finite width, the transm itted m olecules have velocities
in a certain range Av about the given value. W h en either ω or Θ is changed, the
v e lo c ity o f the molecules received at the detectors can be changed. I f one makes
several observations for differen t velocities v, the v e lo c ity and energy distribu­
tions are obtained. T h e experim ental results confirm the prediction o f M a x w ell-
B oltzm an n statistics, as expressed by Eqs. (10.44) and (10.45).
A s explained in Section 8.6, neutrons produced in the fission process in a nuclear
reactor are slowed down by means o f a suitable m od erator until th e y are in therm al

Effusing
gas
Collimated Velocity-selected
beam beam

Gas
Ί I
O
I )etector

Kotatiug disks

Fig. 10-8. Molecular velocity selector.

 10.6) Applicalion Io Ihe ideal gas 055

equilibrium a t the tem perature o f the reactor. N eu trons in a therm al nuclear

reactor then behave as an ideal gas and th eir energy distribution agrees w ith
M a x w e ll’s law, E q. (10.44); th at is, therm al neutrons follow M axw ell-B oltzm an n
statistics. T h is fact is essential in nuclear reactor design. I f the neutrons em erging
from a porthole in a reactor are m ade to pass through a chopper sim ilar to th at o f
Fig. 10-8, a m onoenergetic beam o f neutrons is obtained.

E X A M P I-H 10.7. Obtain the most probable energy and velocity of the gas molecules
at a given temperature; these values correspond to the maxima of dn/dE and dn/dv,
respectively.

S o lu tio n : T o obtain the maximum of dn/dE, given by Eq. (10.44), at a certain tempera­
ture, it is necessary to compute only the maximum of y = E '/2e~K/kT. Thus

from which we have E mv = ^ k T . Thus at room temperature, for which k T ~ 0.025 eV,
we have E m,, ~ 0.012 eV.
Similarly, to obtain the maximum of dn/dv, given by Eq. (10.45), we must compute
the maximum of y = v2e~m’~,2kT. Then

Therefore t>mp = V 2kT/m. This velocity corresponds to an energy E = k T and is there­

fore different from E mv. Oan the student explain the reason for this difference?

E X A M P L E 10.8. Average velocity (Cavc) and root-mean-square velocity (erms) of the

molecules in an ideal gas.

' S o lu tio n : The average velocity is defined by

Introducing the value of dn/dv given by Eq. (10.45), we have

W c first transform the integral by setting u — v2, so that du = 2c dv, resulting in

r CO

* /.

N ext we integrate by parts, resulting in %(2kT/m)2, so that

45β Classical statistical mechanics

lit!
dr

F ig. 10-9. Most probable, average,

root-mean-square velocities of a
and root-i
gas.

O V

We define the root-mean-square velocity by = (a2)»,», and we obtain the average

of-a2 from the expression

N oting that a2 = 2E/m, we may also write

since the average energy is defined by 2?llvo = (1 / N )J E dn. But for an ideal gas, accord­
ing to Kq. (10.44), irVve = ^ k T . Thus

2 _ , 2. _ 2 , 3, ™ . _ 3kT
Crms — (a )avo ( 2k T )
m m
and

The three velocities, t>mp, I1avc, and rrmB arc indicated in Fig. (10-9).

H v ie rv n e e s

1. “ What is Probability?” It. Carnap, Sci. Am ., September 1953, page 128

2. “ Thermodynamics, Statistics, and Information,” L. Brillouin, Am. J. Phys. 29, 318
(1961)
3. "The Work of Τ . II. Berlin in Statistical Mechanics,” M . K ac1 Physics Today, Octo­
ber 1964, page 40
4. “ New Approach to Statistical Mechanics,” It. Weinstock, Am. J. Phys. 35, 710
(1967)
5. Statistical Mechanics, G. Rushbrooke. London: Oxford University Press, 1949
6. Statistical Physics, G. Wannier. New Y ork: John Wiley, 1966, Chapters I, 2, and 3

7. Fundamentals of Statistical Thermodynamics, R. Sonntag and G. Van Wylen.
Y ork: John W iley, 1966, Chapters I and 2
8. Statistical Thermodynamics, E. Schrodinger. Cambridge: Cambridge University Press,
1964, Chapters I and 2
9. The Fcynynan Lectures on Physics, Volume I, R. Feynman, R. Leighton, and M . Sands.
Reading, Mass.: Addison-Wesley, 1963, Chapter 40
I t T o b iv m M
10.1 Referring to Example 10.2, find the
change in the probability of the distribu­
tion if two particles, one from the upper
and one from the lower level, are trans­
ferred to the intermediate level. Repeat
for the most probable partition found in
Example 10.3.
10.2 In Example 10.2, compute the ratio
P 2 / P 1 , using Eq. (10.13) for In P .
10.3 Determine the temperature of the
system of Example 10.3 when it is in sta­
tistical equilibrium. Assume e = 0.02 cV.
10.4 Find the ratio of the number of elec­
trons having their spins parallel and anti-
parallel to a magnetic field as a function of
the temperature. Evaluate the number for
a temperature T equal to 10°, 300°, and
IOOO0K. I H int: Recall that the spin mag­
netic moment of the electrons is given by
M s = -2 / ib S1 Eq. (3.33).)
10.5 (a) Show that the partition function
of an electron gas placed in a magnetic
field ffi is Z = 2 cosh (μηffi/AT), where μη
is a Bohr magneton, (b ) Compute the
magnetic energy of an electron gas in the
magnetic field; then show that the para­
magnetism of free electrons corresponds to
a magnetization M = ημη tanh (μηffi/fcT),
where n is the number of electrons per unit
volume, (c) Find the limiting values of
the partition function and the mag­
netization at very low and very high
temperatures.
10.6 The possible particle energies of a
system of particles are 0, e, 2e, . . . , «e, . . .
(a) Show that the partition function of the
Problems 457
N ew
system (with g, = I) is
Z = (I - e - ‘,kT) - K
(b ) Compute the average energy of the par­
ticles. (c) Find the limiting value of the
average energy when e is much smaller
than kT.
10.7 Considering a system of particles
having energies 0, e, 2e m , . . . , plot a
graph showing the occupation numbers for
(a) IOO0K, (b ) 300°K, (c) 800°K, given
that the value of the energy t is (a) IO-3 cV,
(b ) 0.1 eV. [H int: Use the result of Prob­
lem 10.6 for the partition function.]
10.8 The magnetic moment of atoms (or
molecules) having an angular momentum
J is given by Eq. (3.40): M = —y iig j.
(a) Obtain an expression giving the num­
ber of atoms having a value of J , equal to
mh, if the atoms are placed in a magnetic
field ffi oriented parallel to the Z-axis. (b)
Show that the partition function of the
system of atoms is
^ = sinh [ ( j + ^Vugffi/AT]
sinli ligBjffi/fcTI
(c) Verify that for j = £ the partition
function reduces to that obtained for elec­
trons in Problem 10.5.
10.9 Obtain the average magnetic energy
of the atoms considered in the preceding
problem. Verify from this result that the
average magnetic moment of the atoms in
a direction parallel to the magnetic field is
• U a VO
= μ IIffIO ' τ £ ) COth 0 - f £ ).r — £ cot.li £ j ]
 45S Classical statistical mechanics
\
where x = Find the limiting
values of .Uavc for x very small and very
large compared with I.
^-10.10 A t what temperature is the number
of molecules of an ideal gas per unit energy
range at 2 X IO-2 eV, one-fourth of the
number corresponding to I X IO-2 eV?
10.11 Find the ratio of the number of
molecules of an ideal gas per unit energy
range at energies of 0.2 eV and 0.02 eV,
given that the gas temperature is (a) 100°K,
(b) 300°K , (c) OOO0K.
10.12 Compute enough points to con­
struct graphs of the molecular energy dis­
tribution function in an ideal gas for one
kilomole at 200°K and OOO0K.
10.13 (a) Compute the root-mean-square,
average, and most probable velocities of
oxygen molecules at a temperature of
300°K. (b) Compute the most probable
velocity of oxygen molecules at the follow­
ing temperatures: 100oK, 300°K, 1000°K,
10,000°K.
10.14 (a) Compute the mean translational
kinetic energy of an ideal gas molecule at.
300°K. (b) Compute the root-mean-square
velocity if the gas is hydrogen (H 2), oxy­
gen (O 2), or mercury vapor (H g ). Compare
your results for hydrogen and oxygen with
the velocity of sound in those gases.
10.15 Compute the root-mean-square ve­
locity of (a) helium atoms at 2°K, (b)
nitrogen molecules at 27°C, (c) mercury
atoms at 100°C.
10.16 A t what temperature is the mean
translational kinetic energy of a molecule
of an ideal gas equal to that of a singly
charged ion of the same mass that has
been accelerated from rest through a po­
tential difference of (a) I volt, (b ) 1000
volts, (c) 1,000,000 volts? Neglect relati­
vistic effects.
-10.17 Determine the fractional number of
molecules of an ideal gas with velocities
between Cavc and l.2i’avc from Kq. (10.45)
making (a) v = Cavc and dv = 0.2ravc; (b)
V = 1.1 Iiav,. and dv = 0.2i'avc.
10.18 Show that the number of molecules
of an ideal gas moving with velocity having
components in the range vz and vz + dvz,
vu and Vy -f- dv„, v; and c. -(- dv-, is given by
dn = N (m /2 n kT):i,~e~”" l2lcT dvz dvu dvt.
[Note that, in Kq- (10.45), for this case we
must replace the integration element
4irD" dv by dvz dvu dvz. Justifjr this re­
placement.]
10.19 Show that the number of mole­
cules of an ideal gas that have an X -
component of velocity between vz and
vz -\- dvz irrespective of the values of the
vu and vz components is
dn = N (m / 2 T k T )u2e~mt‘ ,2kT dvz.
[H in t: Integrate the expression obtained in
Problem 10.18 over c„ anil Cj . The limits
of integration in each case must be from
— 00 to +00 .)
10.20 Use the result of Problem 10.19 to
obtain the average value of (a) C1, (b ) vz,
(c) Ic1I for an ideal gas.
10.21 The error function erf (x) is defined
by
In Table 10-1 we give some values of this
function. Using the result of Problem 10.19,
show that the number of molecules of an
ideal gas having an .Y-component of veloc­
ity between 0 and C1 is
A'(0, Vz ) = N erf (x),
where x = ( m /2kT)l,2vz, and the number
of molecules having an .Y-component of
velocity larger than c* is
N (v z, » ) = A:[ i — erf (* )].
10.22 What fraction of the molecules of an
ideal gas have positive .Y-components of
velocity greater than 2cmp?
 Problems 459

TABLE IO-I Values o f c r f (*)* 10.28 Using the result of Problem 10.25,
find the percentage of molecules of an ideal
X erf (x) X erf (x) g a s that have an energy larger than 0.5 eV,
given that the temperature is (a) 300°K,
0 0 1.6 0.4882 (b) 600°K, (c) 1,000°K. IH int: Note that
0.2 0.1113 1.8 0.4946 in the expression derived in Problem 10.25,
0.4 0.2142 2.0 0.4977 x = (E / k T )U2.]
0.6 0.3019 2.2 0 4991
10.29 Show that the number of gas mol­
0.8 0.3711 2.4 0.4996
ecules with velocity between v and e + dv
1.0 0.4214 2.6 0.4999
colliding with the wall of a container, per
1.2 0.4552 2.8 0.5000
unit area and per unit time, is £v(dn/dv) dv.
1.4 0.4762 3.0 0.5000
Then show that the total number of mol­
* For larger values of x, the values of ecules colliding with the wall per unit time
erf (x) remain constant at 0.5000, up to is i ne0vc where n in both cases refers to the
four significant figures. number of molecules per unit volume.
N ote that the molecules with velocity v
colliding per unit area and per unit time
10.23 Compute the fraction of molecules and moving in a direction making an angle
of an ideal gas that have a velocity with a Θ with the normal to the wall are those
component along the X-axis (a) smaller within a cylindrical volume of height
than ΐ’,ηρ, (b ) larger than Vmvi (c) smaller equal to t 'cos 0. Also the fraction of mol­
than Have, (d ) larger than Covc. [ H int: See ecules moving within the solid angle dU is
Problem 10.21.]
10.24 What fraction of the molecules of
■ I ^dvdSl and dV. = 2ir sin 0 <10.
an ideal gas have X-components of veloc­ 4ir dv
ity between - V mp and + I i mp?
10.30 Assume that a small hole is made in
10.25 Show that Jthe number of molecules
the wall of an oven containing a gas at
of an ideal gas that have a velocity be­
temperature T. Show that the number of
tween zero and v is given by
molecules with velocity between v and
v -+· dv escaping per unit area and per
X (0, i’) = 2N erf ( x ) xe x~ unit time is
V ir
J m λ 3' 2 3 —m -j 2kT
where x2 = mv2/'2kT. Also find the num­ dn v e dv,
ber of molecules that have a velocity
larger than v. [H in t: Use Eq. (10.45) and
where N gives the total number of mole­
integrate by parts.]
cules per unit volume in the oven. Find
10.26 Using the result of Problem 10.25, the total number of molecules escaping
compute the fraction of molecules of an per unit, area and per unit time. Also
ideal gas that have a velocity (a) smaller show that the average and root-mean-
than (b ) larger than emp, (c) smaller square molecular velocities in the outgoing
than I10Vc (d ) larger than cavc· beam are
10.27 What percentage of oxygen mole­
3 h irk T
cules have velocities greater than IO3 m s_ l
at a temperature of (a) 100°K, (b) l,000oK,
I'ave — ο Λ I
8 \ m
(c) 10,000°K? Illustrate graphically in and
terms of the distribution function. vrm, = V ik T / m .
460 Classical statistical mechanics
Compare with the corresponding values
for the molecules inside the oven and make
a critical evaluation of the results of the
experiment illustrated in Fig. 10-8. [H int:
Use the results of the preceding problem ]
10.31 (a) Show that the deBroglie wave­
length for a particle of mass m moving
with the most probable velocity of a max-
wellian distribution at temperature T is
λ = h / (2 m k T )112, where k is Boltzmann’s
constant. (b ) Calculate the deBroglie
wavelength of a neutron moving with the
most probable speed of a maxwellian dis­
tribution at 20°C. Compare these wave­
lengths with the interatomic separation in
a solid.
10.32 W hat fraction of (a) II atoms, and
(b ) HCl molecules would be in the first
excited state at 300°K?
10.33 Suppose that the energy of the mol­
ecules of a system can be expressed as a
sum of two terms; that is,
Li — Ei,a Hi.int
where E i,u refers to the translational motion
and F,. ini refers to the internal degrees of
freedom (such as the rotation and vibra­
tion of a molecule), or to the interaction
with an electric or magnetic field. If Jlltr
and ffi,i„t are the intrinsic probabilities cor­
responding to both types of motion, we
have that g, = gi.trff,.i„t. Show that: (a)
Z = Z trZim, where Z is the total partition
function and Z tr and Z ;„t are the transla­
tional and interval partition functions;
(b ) U = U a + U i n f
 11

THERMODYNAMICS

11.1 Introduction
11.2 Conservation o f Energy o f a System o f Particles
11.3 M a n y -P a rticle Systems; W ork
l l /ι M a n y -P a rticle Systems; I I eat
11.5 The First Law o f Thermodynamics
11.6 Graphical Representation o f Processes
11.7
11.8 E ntropy and the Second Law o f Thermodynamics
11.9
11.10 Discussion o f Processes in Terms o f Entropy
462 Thermodynamics ( 11.2

11.1 In iro d u v tio n

I n C hap ter 10 w e developed a statistical m odel for handling systems o f m any
identical com ponents; this was called M axw ell-B oltzm an n statistics. W e illus­
trated this m odel by ap plyin g it to a special exam ple o f noninteracling particles:
the ideal gas. B u t the particles w e find in nature are always interacting am ong
them selves. T h u s the next step is to discuss assemblies o f interacting particles,
such as atom s or m olecules in the solid, liquid, or vap or state, or even the nucleons
in a nucleus. E qu ally im portant, we w ant to establish a correlation between the
predictions o f statistical mechanics and the quantities we measure or observe ex­
perim entally at the macroscopic level. Also, instead o f considering an isolated
system in statistical equilibrium , we w ant to find w hat happens when a system
interacts w ith its surroundings, since this is the situation th at is m ost com m on in
nature.
T h is gap between statistical mechanics and the m acroscopic properties o f m at­
ter is bridged by th e branch o f physics called thermodynamics. H istorically, the
science o f therm odynam ics developed during the eighteenth and nineteenth cen­
turies (b efo re the introduction o f statistical m ethods) when the notions o f heat and
tem perature were not y e t well understood. I t e v o lv e d as a rather form al and ele­
gant th eory whose results and m ethods became extrem ely im portant fo r engineer­
ing purposes, due to the d evelopm ent o f heat engines at about the same time.
Therm odyn am ics reached its clim ax at the end o f the nineteenth century, w ith the
w ork o f C arnot, Joule, K e lv in , and others, just a t the tim e when statistical m ethods
were beginning to be introduced through the work o f M a y er, Boltzm ann, Gibbs,
and others. T h e d evelopm ent o f statistical m ethods and their application to
chem ical processes have m ade a revision o f the form ulation o f therm odynam ics
necessary. H o w ever, from the point o f view o f its applications, no essential changes
have been introduced.
In this chapter we shall consider therm odynam ics from the point o f v ie w of
statistical mechanics.

11.2 V on svrra iion o f En vrffy o f a S ysivm o f E a riivlvs

L e t us consider a system o f particles subject both to their m utual interactions and
to external forces. T h e system m ay, for exam ple, be a single hydrogen m olecule
(in which case the com ponent particles are tw o protons and tw o electrons) or a
gas containing a large number o f hydrogen molecules. In the latter case, the par­
ticles com posing the system are the m olecules; thus their internal structure m ay
be ignored in a first approxim ation. G iv e n th at E p y is the poten tial en ergy due
to the interaction o f particles i and j , the internal potential energy o f the system is

E p in t = ^ ff l F p ij = E p H + E pl3 + · · ■+ E P23 + ■ · ■ (IL l)

All
p airs

S im ilarly, let us designate the sum o f the kinetic energy o f the particles referred
11.2) Consermlion of energy of a system of particles 463

to the center o f mass o f the system * as internal kinetic energy; th at is,

E k im = Jwi,-i>? = Jw iiyf + Jwi2i’2 T - JwiailI + · · · (11-2)

AU
p a r tic le s

N o te th at E q . (11.2), corresponding to the kinetic energy, has one term fo r each

particle, while E q . (11.1), corresponding to the poten tial energy, has one term for
each p a ir o f particles, because it refers to tw o-p article interactions on ly. T hen the
total internal energy U o f the system is

U — Ek in t + E p in t . (1 1.3)

F o r the case o f an ideal gas, there are no interm olccular forces and the internal
energy is just the kinetic energy. In some instances the potential energy can be
expressed as a sum o f single-particle terms, as indicated in Section 10.2. T h is is
possible when, to a first approxim ation, the interparticle potential energy can be
replaced b y an average potential energy for each particle. I f no external forces
act on the particles o f the system (i.e., if the system is isolated from external
actions), then U does not change. In other words:

The internal energy o f an isolated system o f particles remains constant.

W hen there are external forces actin g on the particles o f the system , the internal
energy docs not, in general, rem ain constant. Suppose th at the system is in itially
in a state w ith internal energy U 0. T h e state o f the system is continuously m odi­
fied b y the external forces, so th at a fter a certain tim e the internal energy is U .
L e t us designate the total w ork done during the same tim e b y the external forces
acting on the particles o f the system by W ext. T h e w ork W ext is a sum o f m any
terms, one for each particle subject to an external force. T h e n conservation of
energy requires that

U - U 0= W ext, (11.4)

which states th at:

The change in the internal energy o f a system o f particles is equal to

the work done on the system by the external forces.

I t m ay happen that, even if there are external forces acting on the system, their
total w ork is zero: W cxt = 0 . In such a case there is no change in internal en ergy;
th at is, U = U 0. I f w ork is done on the system (W ext positive), its internal energy
increases ((/ > U 0), but if work is done by the system (W ext n egative), its inter­
nal energy decreases ( U < U 0).

* T o express the kinetic energy, we have to define a frame of reference, since otherwise
its value is indeterminate.
 I

d6d Thermodynamics (11.3

ll.it M a n y -P a r t ie le S ystem *; W o r k
T h e system s w e consider in therm odynam ics are com posed o f a v e ry large number
o f particles, and therefore calculating the external w ork as a sum o f individual
works on each particle poses serious difficulties. F o r th at reason it has been found
convenient to express IF ext as a sum of tw o terms, both o f a statistical nature.
One is still called work and the other is called heat. V e ry often, especially when
w e are dealing w ith therm al engines, it is preferable to com pute the external w ork
done by the system , denoted b y IF syst, instead o f the external w ork done on the
system , IF ext. Since both works correspond to the same displacem ent but to
forces equal and opposite, the tw o works are equal in m agnitude but h ave op p o­
site signs; th at is, IF syst = - T F ext. In the future we shall w rite TF instead o f
TFsyst fo r the w ork done by the system.

F ig. 11-1. W orkdoneduringexpansion

of a gas.

Consider, for exam ple, a gas inside a cylin d er (F ig . 11-1). T h e gas can exchange
energy and m om entum with the surroundings through the collisions and interac­
tions o f its m olecules w ith the molecules o f the walls. T h e exchange of m om entum
is represented by a force exerted by each m olecule at the point o f collision w ith
the wall. These individual forces fluctuate at each point, but because there are a
great m any collisions o v e r a large area, the overall effect can be represented b y
an average force F acting on the whole area. T h e pressure p o f the gas is defined
as the average force per unit area. Th en , given that .4 is the area,

p = F/A F = pA. (11.5)

I f one wall o f the container is m ovable, such as the piston o f Fig. 11-1, the
force exerted by the gas m ay produce a displacem ent dx o f the w all. T h e exchange
o f energy o f the system w ith the outside w orld m ay then be expressed b y the
w ork done by this force during the displacem ent. T h erefore

dW = F dx = p A dx = p dV, ( 11.6)

where d V = .4 dx is the change in volum e o f the gas. Th en , if the volum e changes

from V 0 to V , the external work done by the gas during the expansion w ill be

W = Γ pdV. (11-7)
Jv0
 Many-particle systems; work 465

T o com pute this integral, we m ust know the relation between p and F. T h is rela­
tion has been studied in great detail fo r gases and other substances, and we shall
consider it later 011.
O bviou sly the external work done on the gas is

Wt x l = - T p d V . (1 1 .8 )
I Vo

L e t us now recall some o f the more com mon units in which pressure is expressed.
N o te first th at pressure must be expressed as a unit o f force d ivided by a unit of
area. T h u s in the M K S C system , pressure is measured in newtons per square meter,
or N m - 2 . O th er units frequ en tly used are dynes per square centimeter (d yn cm - 2 ),
and pounds-force per square inch (lb f in - 2 ). A n o th er useful unit, used m ainly for
expressing the pressure o f gases, is the atmosphere, ab b reviated atm , and defined
according to the equivalences

I atm = 1.013 X IO5 N m - 2 = 14.7 lb f in - 2 .

One atm osphere is ap p roxim ately the norm al pressure exerted by the earth ’s
atm osphere on bodies at sea level.

E X A M P L E 11.1. A gas occupies a volume of 0.30 m3, exerting a pressure of 2 X IO5

N m -2 . The gas expands to a volume of 0.45 m3, while the pressure remains constant.
Find the work done by the gas.

S o lu tio n : W e use Kq. (11.7) and, when the pressure p remains constant,

1Γ = Γ pdV = p
Jv0 Jv0
CdV = p (V - F 0). (11.9)

This result is completely general and applies to any system whose volume changes under
a constant pressure. Inserting the numerical values, we obtain

11' = 3 X IO4 J.

E X A M P L E 11.2. A gas expands in such a way that the relation p V = C (constant)

holds. This relation requires that the temperature of the gas remain constant, and con­
stitutes Boyle’s law. Find the work done when the volume expands from T i to F 2.

S o lu tio n : Using Eq. (11.8), we obtain

1 '° f <1U
0)
Therefore the work done depends on the ratio F 2/ F 1 between the two volumes (this is
called the expansion ratio). In the design of internal combustion engines, thecompression
(or expansion) ratio is one of the factors which determine the power of the engine.
466 Thermodynamics (11.4

11.4 HIan y - P a rticle SyHtvmn; Mlvat

I t is im portant to bear in m ind th at E q. (11.7) expresses a macroscopic average

which sums all the individual exchanges o f energy between the m olecules o f the
gas and the molecules in the piston. Hut how does one com pute the exchange of
energy which occurs due to the interaction o f the gas molecules w ith the walls th at
rem ain fixed? In this case the m ethod used to evalu ate W fo r the piston does not
apply. A lth ou gh w e m ay still define an average force on the wall, w e cannot define
an average displacem ent of the wall. A t each individual interaction between the
molecules of the gas and the wall, a small force is exerted and a small displacem ent
o f the m olecules in the wall is produced. I f we could com pute each one o f these
infinitesim al amounts o f work and add all o f them, we would have the correspond­
ing external work done by the system. H ow ever, this technique is ob viou sly al­
m ost im possible because of the large number o f factors involved. Thus w e shall
define a new m acroscopic or statistical concept called heat to account for such work.
T h e average value o f the external w ork or energy exchanged between a system
and its surroundings due to the individual exchanges o f energy which occur as a
result o f collisions between the m olecules o f the system and the m olecules o f the
surroundings is called heat, Q, w h enever it cannot be expressed m acroscopically
as force tim es distance. T h erefo re Q is com posed o f a sum o f m any v e ry small
individual external works, such th at they cannot be expressed co lle c tiv e ly as an
average force tim es an average distance.
A ccord in g to the sign convention we have adopted, the heat Q is considered
p ositive when it corresponds to a net external work done on the system and nega­
tiv e when it is equ ivalent to a net external w ork done by the system . In the first
case we say that heat is absorbed by the system and in the second case w e say th at
heat is given off b y the system.
Since heat corresponds to work, it m ay be expressed in joules. H ow ever, heat
is often expressed in a unit called the calorie, ab b reviated cal, whose definition was
adopted in 1948 as I calorie = 4.1840 J. T h e calorie was first· introduced as a unit
o f heat m easurement when the nature o f heat was not clearly understood. B u t the
calorie is sim ply another unit for m easuring work and energy, and not heat alone.
A t this point we must warn the student not to consider heat as a new or d iffer­
ent form o f energy. I t is just a name given to a special form of w ork or energy
transfer in which a v e ry large number o f particles participate. B efo re the concepts
o f interactions and o f the atom ic structure o f m atter w ere clearly understood,
physicists had classified energy into tw o groups: mechanical energy, corresponding
to kinetic and gravitation al potential energy, and nonmechanical energy, d ivid ed
into heat, chem ical energy, electrical energy, radiation, etc. T h is division is no
lon ger justified. N ow ad ays physicists recognize on ly kinetic and poten tial energy,
w ith potential energy being denoted by a d ifferent expression depending on the
nature o f the corresponding physical interaction, and w ith heat and radiation be­
ing expressions o f tw o mechanisms o f energy transfer. Chem ical energy is just a
m acroscopic term used to describe energy associated w ith electrical interactions in
atom s and molecules, energy which manifests itself in chemical processes; th at is,
as atom ic rearrangem ents in molecules.
11.5) The first law of thermodynamics 467

11.5 T h e Firtti L a ir o f Therm odynam irH

In the previous tw o sections w e have seen that, when w e arc dealing w ith system s
composed o f a v e ry large number o f particles, we should express the total external
work as the sum o f tw o parts: Q + IVcxt. H ere IVcxt expresses the external w ork
when it can be com puted as an average force tim es a distance, as discussed in
Section 11.3, and Q represents the external work when it must be expressed as
heat, as discussed in Section 11.4. E qu ation (11.4) for the principle o f conserva­
tion o f energy must then be w ritten in the form

U - U 0 = Q + IV cxt, (11.11)

which m ay be expressed in words by saying th at

the chantje o f internal energy o f a system is equal to the heat absorbed

plus the external work done on the system.

E qu ation (11.11) can be seen p ictorially in Fig. I l- 2 ( a ) : H e a t Q is absorbed by the

system and w ork IVcxt is done on the system. T h e ir sum Q + IV cxt is stored as inter­
nal energy U - U 0 o f the system. Som etim es, especially in engineering applica­
tions, w e do not w rite the external work IVcxt done on the system, but the external
w ork IV done by the system ; as explained before, this is the negative o f the w ork
done on the system. S ettin g IVcxt = — IV, we have, instead o f Eq. (11.11),

U - U 0= Q - W . (11.12)

E qu ation (11.12) is illustrated in F ig. l l - 2 ( b ) : H e a tQ is absorbed by the system ,

w ork IV is done by the system , and the difference Q — IV is stored as internal en ergy
U — U o o f the system.

(a) (I.)

F ig. 11-2. Relation between heat, work, and internal energy.

T h e statem ents related to Eqs. (11.11) and (11.12) constitute what is called the
first law o f thermodynamics, and is sim ply th e law o f conservation o f energy applied
to system s h a vin g a v e ry large number o f particles, w ith the external w ork con­
v e n ien tly split into tw o statistical terms, one still called work and the other called
heat.
W e m ay n ote th at because o f its definition, the internal energy o f a system depends
only on the state o f the system, w hether or not it is in equilibrium , and it does not
depend on h ow the system reached that state. H o w ever, only when the system is
in a state o f equilibrium and the particles com posing the system ob ey M a x w ell-
468 Thermodynamics (it.5

B oltzm an n statistics can Eq. (10.24) be used to com pute U\ that is,

U = k N T 2~ (\ n Z ).

On the other hand, the w ork W and the heat Q are quantities d irectly related to
the process th at the system experiences when it goes from the initial to the final
state. T h a t is, when the system goes from a given in itial state to a given final state,
several processes m ay be possible. For all the processes connecting the same states,
the values U 0 and U o f the initial and final internal energy are the same, so th at
the difference A U = U — U 0 is independent o f the process. B u t the values o f the
heat Q and the w ork IF in general are different for each process. In other words,
the division o f the energy exchange into heat and work depends on the process.
A n especially interesting case occurs when the system undergoes a cyclical
transformation, or sim ply a cycle.
T h is means th at a t the end o f the process the
system returns to its initial state. T h erefore

U = Uq and A U — U — U 0 = 0,

which, when substituted in E q . (11.12), yields

Q=W. (11.13)

T h u s in a cycle the heat Q absorbed by the system is all transform ed into w o rk W

done b y the system. T h is is just the operating principle of therm al engines, whose
purpose is to absorb heat and perform w ork in a cyclical fashion.
I f the transform ation suffered by a system is infinitesim al, we must replace
AU = U - U 0 b y dU, Q b y (IQ, and IF by (IW in E q. (11.12). W hen we do this,
w e obtain the follow in g expression:

dU = dQ - dW . (11.14)

T h is equation expresses the first law o f therm odynam ics in differential form .
N o te th at we are w ritin g dQ and d W and not dQ and dW for the infinitesim al
changes in Q and W. T h e reason we do this is to emphasize that, although U is
a function o f the state and its change depends on ly on the initial and final states,
Q and IF are quantities associated on ly w ith processes. In m athem atical language,
we say th at dU is an exact differential o f the variables used to define the state of
the system , while dQ and d W are not.
W h en the work dW is due to an expansion or change in volum e, we have from
E q. (11.8) th at dW = p d V , and Eq. (11.14) becomes

d U — dQ — Tp dV. (11.15)

B u t we warn the student th at there m ay be other kinds o f w ork in addition to

expansion, yield in g different expressions in term s of the variables o f the problem .
F o r exam ple, if a charge dq is m oved by em f F e, we must w rite dW = F e dq.
 Graphical representation of processes 469

Il.G G ra phical Kcprcxcntation o f Proeeeaee

T o describe m acroscopically the state o f equilibrium o f a system o f atom s or m ol­
ecules, we use some m acroscopic or statistical parameters. T h e m ost usual ones
are the pressure, the tem perature, and the volum e. W e could also use the total
internal energy, but this is not com mon. I f the system is composed of tw o or m ore
independent substances, in order to com p letely specify the state o f the system, we
must also know th eir rela tive proportions.
T h e m acroscopic or statistical variables describing the state o f a system in
equilibrium are not all independent; th ey are related by a m athem atical expression
called the equation o f state, which is characteristic o f the physical structure o f the
system. F o r exam ple, the equation o f state o f an ideal gas (see Section 12.2) is

pV = nRT, (11.16 )

where N is the number o f moles and R is the gas constant defined in E q. (10.43).

One o f the most im portant problem s o f statistical physics is to derive the equa­
tions o f state fo r d ifferent kinds o f substances, since a knowledge o f the equation
o f state is o f immense theoretical and practical im portance.

L e t us designate the equation o f state o f a single homogeneous substance by

f (p , V , T ) = 0. W e m ay represent this function b y a surface called a thermo­
dynamic surface, using a set o f axes labeled p, V , and T (F ig . 11-3). A particular
equilibrium state o f a system, characterized b y certain values o f p, V , and T , is
represented b y a point S on the surface. I f the system undergoes a process or trans­
form ation it even tually passes to another equilibrium state S ', also on the surface.
In general, the interm ediate states occupied in the transform ation S —> S 1 are not
equilibrium states and cannot be represented b y points on the surface

}{ p , V , T ) = 0.
470 Thermodvnamics (11.β

F ig. 11—i. Reversible expansion and compression of a gas.

H o w ever, if the transform ation occurs v e ry slow ly (proceeding at all tim es by

infinitesim al steps, so that at each step the system is on ly sligh tly disturbed from
its state o f equilibrium ), we m ay reasonably assume that the system at each in­
stant is in statistical equilibrium . A transform ation of this kind is said to be
reversible.
W e m ay use the expansion o f a gas to illustrate a reversible transform ation.
Suppose th at the piston in Fig. 11-4 is held in position by m any sm all weights, as
indicated in Fig. l l - 4 ( a ) . A t equilibrium the pressure o f the compressed gas is
equal to the pressure due to the weights plus the atm ospheric pressure. I f we re­
m ove one of the weights, by sliding it to one side on to a platform , the external
pressure decreases by a small am ount and the equilibrium o f the gas is sligh tly
disturbed. T h e gas then undergoes a small expansion until equilibrium is (q u ic k ly )
restored. W hen the process is repeated a number o f times, the gas even tu ally
expands up to the volum e shown in (b ) and the weights, which were previou sly on
to p o f the piston, are stored as shown. Since the process has occurred v e ry slow ly,
w e m ay assume th at the gas has rem ained continuously in statistical equilibrium
and th at the expansion has been reversible. T o restore the gas to the initial state,
all we have to do is to place back, in the reverse order, the same w eights we took
off. A t the end the gas is in its initial state, havin g com pleted a cycle, and no
change has been produced in the surroundings. In other words, in a cycle entirely
composed o f reversible transformations, it is possible to arrange things so that no ob­
servable change is produced cither in the system or in the surroundings.
O n the oth er hand, an irreversible process occurs when the system d evia tes to a
great exten t from the equilibrium state. D u rin g the process such statistical quan­
tities as pressure and tem perature are undefined. E ven tu ally, a t the end o f the
process, the system returns to equilibrium in a new state characterized b y a cer­
tain pressure and tem perature. In general, irreversible processes occur at great
speed. W e m ay again use the expansion o f a gas to illustrate an irreversible process.
T h e gas in Fig. I l- 5 ( a ) is as it was in F ig. 11- 4 (a ), b u t with all w eights consolidated
in to one, labeled .4. N o te th a t there is also a weight B at the upper level. If
11.6) Graphical representation of processes 471

JflI

ώ
F ig. 11-3. Irreversible expansion and compression of a gas.

w eight A is suddenly rem oved, the external pressure suddenly drops and the
gas expands rapidly, w ith a great turbulence in its m olecular m otion ; i.e., the
process is irreversible. Ilu rin g the process th e m olecular velocities do not follow
the M axw ell-B oltzm an n distribution law. F in a lly the piston comes to rest a t a
certain position and even tu ally equilibrium is restored, w ith w ell-defined pressure
and tem perature, as indicated in F ig . 11—5 (b ). T o take the gas back to its in itial
state, w e m ay m ove weight, B to the top o f the piston, which then m oves down in
a process which m ay or m a y not repeat, in reverse, the previous process. In the
end, when equilibrium is once more restored, the gas is again in its initial state,
as shown in F ig. 11—5 ( c ) ; the gas has com pleted a cycle. H ow ever, a definite
change has occurred in the surroundings. W e ig h t B, which was in itia lly a t the top,
is now a t the b ottom . Thu s: I n a cycle composed, in part or in total, of irreversible
transformations, the system returns to its initial state, but a finite measurable change
is produced in. the surroundings.
I t is clear th a t a reversible transform ation can be represented b y a line on the
therm odynam ic surface }{p, V, T ) = 0, join in g the in itial and final states S and
S ', but an irreversible process cannot be represented in such a way.
T h e three parameters p, V, and T are not independent, since they are related b y
the equation o f state f(p , V, T ) = 0. T h e refo re in general it, is necessary to use
on ly tw o coordinates to represent a given process. A com m on case, especially fo r
gases, is to use a p -V diagram . F o r exam ple, in Fig. 11-0, a reversible transform a­
tion from state A with pressure p i and volu m e V i to state B w ith pressure p 2 and
volu m e F 2 is represented in a p -V diagram . T h e tem perature at each instant is
obtained from the equation o f state. T h e p -V diagram is especially useful for
gaseous processes because th ey bear a close relationship to the w ork done b y th e
gas. R e ca llin g E q. (11.7), we note that p d V is th e area o f a strip o f w idth dV and
height p, and therefore the w ork done b y the system in goin g from A to B by a
certain process is g iven b y
r.
un Thermodynamics (11.6

F ig. 11-6. Diagram of a reversible pro­ F ig. 11-7. The work done in going from
cess in the p -V plane. The work done by the state A to state B depends on the process
system is indicated by the shaded area. followed by the system.

T h e w o rk done is then the area under the curve A B in Fig. 11-6, corresponding to
the transform ation. T h is helps us understand w hat was said in Section 11.5 about
the w ork depending on the process. F igu re 11-7 indicates several processes, cor­
responding to curves ( I ) , (2 ), and (3 ), all o f which take a system from state A to
state B . Since the area under each curve is different, the w ork done in each process
is also different. T h e initial and final states are the same for the three processes,
and thus the change A U = U a - U b 111 internal energy is the same in each case.
T h erefo re the heat corresponding to each process, given b y Q = A U + W, w ill be
different. I f the process is irreversible, it cannot be represented in a p - V diagram ,
and the calculation o f the w ork is more difficult.
L e t us next consider a cycle, in which the system goes from A to B (F ig . 11-8)
along process ( I ) and returns from B to A along process (2 ). In goin g from A to
B it does a w ork equal to the area under curve ( I ) . In returning from B to A it
does a w ork equal to the negative o f the area under curve (2 ) because w ork is done

F ig. 11-8. Cycle. The work done by the

system in describing the cycle clockwise is
equal to the area enclosed by the cycle in a
p -V diagram.
11.7) Special processes 073

on the system . T h e net w ork W done by the system during the cycle is thus the
shaded area enclosed within the curve representing the cycle; th at is,

IF cycIe = ^pdV = area under ( I ) — area under (2 ) = area w ith in Α (1 )β (2 ).4 .

A s indicated in Section 11.5, therm al machines do w ork a t the expense o f heat ab­
sorbed in a cyclical process. T h e w ork done per cycle, if the process is reversible,
can be com puted once w e know the p - V diagram o f the cycle. T h is w ork is also
equal to the net heat absorbed b y the system during the cycle.

II. 7 S p rfia l I^rorrssrs

L e t us consider some special processes, lim itin g ourselves to the case in which the
w ork is due to expansion only. T h e n E q. (11.15) holds for an infinitesim al process.
T h a t is, d U = dQ — p d V . A n isochoric transformation is one in which the volum e
remains constant. T h e n d V = 0 and E q. (11.15) reduces to

dU v = d Q v, V = const, (11.17)

where the subscript V is used to emphasize th at this equation holds on ly a t con­

stant volum e. F o r a finite transform ation w e have, integrating E q . (11.17) (o r
from E q. 11.12 w ith IF = 0),

U — U 0 = Q v, V = const.

So, in an isochoric transform ation, the change in internal energy is equal to the
heat absorbed, which is to be expected because there is no external work.
L e t us now introduce the concept o f heal capacity at constant volume C v , which
is equal to the heat absorbed b y one m ole o f the substance per unit change of
tem perature, a t constant volum e. T h u s we can use E q. (11.17) and obtain

( 11 . 18)

where N is the number o f moles in the system . In calculating O U /dT, we must

indicate that V is constant, since we m ay also change the tem perature in other
ways, resulting in a different w ay o f changing the internal energy. In general,
the heat capacity C v is not constant, but varies with the tem perature. Since it is
a characteristic o f each substance, it is an im portant m acroscopic or statistical
quantity.
A n isobaric transform ation is one in which the pressure remains constant. T h en
dp = 0 and we m ay substitute d ( p V ) fo r p d V . Introd u cin g this relation in
E q . (11.15), we have

dU = dQ p — d (p V ) p, p = const,
474 Thermodynamics {11.7

w here the subscript p serves to em phasize th at the equation holds on ly at constant

pressure. T h u s

(IQ p = d U p + d ( p V ) p = d {U p V ) v = dHp, p = const,

(11.19)
where the qu a n tity

II = U + pV (11.20 )
is called the enthalpy o f the system . F o r a finite transform ation, w e have, in tegrat­
ing E q . (11.19),

I I — H 0 = Qp, p = const. ( 11 . 21 )

So, in an isobaric transform ation, the change in enthalpy is equal to the heat ab­
sorbed. T h e w ork done in an isobaric transform ation, according to E q. (11.9), is

Wp = P ( V - V 0). ( 11 . 22 )

T h e heat capacity at constant pressure, Cp, is defined as the heat absorbed b y one
m ole o f the substance per unit change o f tem perature at constant pressure. T h u s

(11.23)

N o te that both heat capacities Cp and Cy arc expressed in J 0K -1 m ole- 1 in the

M K S C system o f units. H o w ever, it is custom ary to use the altern ative unit
c a l ° C -1 m ole- 1 . T h e average heat cap acity o f w ater at constant atm ospheric
pressure is 18.00 c a l ° C -1 m ole- 1 . H istorically, the calorie was first defined as
the energy required to increase the tem perature o f one gram o f w ater (o r -j^ m ole)
by 1°C a t constant pressure.
A n isothermal transformation is one in which the tem perature does not change.
F o r an ideal gas, whose internal energy U = §NI i T depends on ly on the tem pera­
ture, the internal energy does not change in an isotherm al process; that is, d U r — 0.
T h u s E q. (11.14) gives

dQT = dW τ or Qt = W t, fo r an ideal gas only.

T h is relation, w e repeat, is va lid only for the isotherm al transform ation o f an ideal
gas.
A n adiabatic transformation is one in which the system neither absorbs nor gives
up heat. T h en (IQ a = 0, and Eq. (11.14) gives

dUa = - d W a, (11.24)

where the subscript a stands fo r adiabatic. Expression (11.24) indicates th at in

an adiabatic transform ation the w ork is done at the expense o f the internal energy
o f the system . T h u s the tem perature o f an ideal gas (and o f m ost substances)
must decrease during an adiabatic expansion and increase during an adiabatic
compression.
 Entropy and the second law of thermodynamics 475

It.U E n tr o p y anti the Seeontl Etitr o f Therinotiynainies

In C h ap ter 10 we obtained the equilibrium partition o f a system, which depends on
the properties o f the com ponents o f the system and corresponds to the m ost prob­
able distribution o f the molecules o f the system am ong the differen t available
energy states. U n d er such conditions P (o r In P ) is a maximum. I f the system , al­
though isolated, is not in equilibrium , w e m a y assume th at it is in a partition (o r
d istribu tion) o f low er p rob ab ility than the m axim um or equilibrium . In due tim e
it w ill evo lv e , under the interactions am ong its com ponents or molecules, until it
attains the p artition o f m axim um p robability. A t this tim e the system reaches
statistical equilibrium and no further increase in P (o r In P ) is expected, unless the
system is perturbed by an external action.
T o describe this natural trend toward statistical equilibrium b y e v o lv in g tow ard
the p artition o f maxim um probability, the im portant concept o f entropy, S , has
been invented. E n tro p y is defined as

S=A-InP, (11.25)

where the B oltzm an n constant k is introduced for convenience in w ritin g future

m athem atical expressions. T h u s the entropy o f a system is proportional to the loga­
rithm o f the probability P o f the pa rtition corresponding to the stale o f the system.
T h is definition o f en trop y applies to any partition or state, cither o f equilibrium or
noncquilibrium ; this is in contrast to tem perature, which is defined only fo r equi­
librium partitions or states. T h is definition also means that the en trop y o f a
system is a prop erty o f the state o f the system and therefore

the change in entropy o f a system when it goes fro m one slate to another
is independent o f the process followed,

since it is determ ined by the probabilities o f the initial and final partitions. F or
equilibrium states, the en trop y can ob viou sly be expressed as a function o f the
macroscopic variables defining the state. Λ reversible transform ation o f a system ,
isolated or not, in which the en trop y o f the system does not change, is called an
isentropic transform ation.
W hen we have tw o system s w ith probabilities P i and P 2, the total prob ab ility
o f the p artition resulting from the com bination o f the tw o system s is P = P i P 2.
T h u s In P = In P 1 + In P 2 and S = A In P = A In P 1 + A In P 2 = S 1 + S 2. W e
see then that en trop y is an a d d itive quantity. T h is is one o f the reasons w h y the
concept o f en trop y is m ore con ven ien t to handle than the concept o f probability.
K eep in g in m ind our definition o f S and recallin g from Section 10.2 th at the
state o f statistical equilibrium corresponds to the most probable partition, we
conclude th at the entropy o f an isolated system in statistical equilibrium has the
m axim um valu e com patible w ith the physical conditions o f the system . H ence the
on ly processes th at m ay occur in the isolated system after it reaches statistical
equilibrium arc those processes th at are com patible w ith the requirem ent that the
entropy does not change; th at is, dS — 0. T h ese are obviou sly reversible processes,
because the isolated system is in equilibrium . On the other hand, i f an isolated sys-
476 Thermodynamics (11.8

tern is not in equilibrium , it w ill naturally evolve in the direction in which its entropy
increases, since these are the processes th at carry the system tow ard the state of
m axim um p rob ab ility or statistical equilibrium . T h u s the processes that are m ore
lik ely to occur in an isolated system are those for which

dS 2; 0 ; (11.26)

the in equ ality holds when the isolated system is n ot in itially in equilibrium , and
the processes are irreversible.
W e m ay then state the second law o f thermodynamics as follows:

The most probable processes that may occur in an isolated system are
those in which the entropy either increases or remains constant.

T h is statem ent m ust be interpreted in a statistical sense since, in a particular in­

stance, due to the fluctuations in the m olecular distribution, the en trop y o f an
isolated system m ay decrease, but the larger the decrease the less lik ely it is to
occur. T h e variation o f en trop y during the evolution o f the system tow ard equi­
librium m ay thus be represented b y the irregular line in Fig. 11-9.

Kquilibriuin value

F ig. 11-9. Variation of entropy of

an isolated system while the system is
evolving toward equilibrium.
Tim e, t

T h e second law o f therm odynam ics expresses the well-known fact th at in an

isolated system there is a well-defined trend or direction o f occurrence o f processes,
and this trend is determ ined b y the direction in which the en trop y increases.
T ra n sp ort phenomena, such as m olecular diffusion and therm al conduction, are
good exam ples o f processes th at alw ays take place in one direction. In both cases
it m ay be verified th at the en trop y o f the system increases. Diffusion takes place
in the direction in which the concentration tends to be equalized, resulting in a
homogeneous system. T h e reverse process, a spontaneous change o f a homogeneous
system into a nonhomogeneous system, which corresponds to a decrease in Cntropjq
is never observed. F o r exam ple, if a drop o f ink is released at a point A inside a
vessel filled w ith w ater (F ig. 11-lO a), the ink m olecules spread qu ick ly throughout
the w ater, and a fte r som e tim e the w a ter is un iform ly colored (F ig . 11—10c). In
this process the en trop y o f the system has increased. H ow ever, if at a given tim e
the velocities o f all the molecules were exactly reversed, all the ink would even tu ­
a lly collect back at A , resulting in a decrease in entropy. B u t this is ob viou sly an
11.8) Entropy and the second law of thermodynamics 477

F ig. 11-10. Irreversible diffusion of ink in water.

extrem ely im probable occurrence, and so far has never been observed. On the
other hand, there m ay be small fluctuations in the concentration o f ink molecules
at different places, even a fter equilibrium has been reached. B u t these fluctua­
tions, in m ost cases, are not noticeable.
I f a system is not isolated, its entropy m ay decrease b y interaction w ith other
systems, whose entropy must then also change. B u t the total am ount o f all changes
o f en trop y m ade by all systems in vo lved in the process must be in agreem ent w ith
E q. (11.26), w ith dS = 0 holding fo r a reversible process and dS > 0 fo r an
irreversible process.
F o r exam ple, if a com bination o f tw o system s is isolated and the total en trop y
is S = S i + S 2, the processes occurring in the com bined system m ust satisfy

dS — dS\ (IS 2 ^ 0.

T h e en trop y o f one o f the com ponents m ay decrease during a process, but the net
change o f en trop y for the w hole system must be positive or zero.
T h e great im portance o f the second law o f therm odynam ics, as expressed by
E q. (11.26), is th at it indicates those processes which are m ore lik ely to occur in
the universe as a whole. T h erefo re there are m any processes th at could occur
because th ey com ply w ith other laws, such as the conservation o f energy. H o w ­
ever, it is v e ry im probable th at th ey w ill occur, because they v io la te the second
law, or requirem ent (11.26).

E X A M P L E 11.3. Entropy of a system in statistical equilibrium and which obeys

Maxwell-Boltzmann statistics.

S o lu tio n : Recalling expression (10.13) for I n F in Maxwell-Boltzmann statistics, and

recalling that N — n „ we have

S = k In F = k n,· In g,· — ^ m In n, + ^ n ,l
» t' »

= —k 2 ln (W f f i) + IcN· (11.27)
57H Thermodynamics (11.8

But from Eq. (10.23) we have

Taking the logarithm of this equation, we have

Thus Eq. (11.27) becomes

■s = * [ ς η· § + Σ « · ln § + Σ '*·]
L I I I -*

I f we now recall Eqs. (10.1) and (10.2), we finally get

(11.28)

E X A M P L E 11.1. Entropy of an ideal gas in statistical equilibrium.

S o lu tio n : W e know that, for an ideal gas, U = %kNT, and in Eq. (1C.40) we obtained
the partition function of an ideal gas as

„ V(2icm kT)312
h*

Making the substitutions in Eq. (11.28), we obtain

This result is known as the Sackur-Telrodc equation. It can be written in the alternative
form
S = k N In ( vT3/2) + So, (11.29)

where v = V / N is the volume per molecule and all quantities that are not variables have
been included in So] that is,

(2 Trmk)''1'
So ~ 2 kfo ■I k.Y In

E X A M P L E 11.5. The change of entropy of an ideal gas during a free expansion.

S o lu tio n : When a vessel containing a gas is connected with an empty vessel, the gas
undergoes a free expansion. Such a process is irreversible, and equilibrium is destroyed for
a certain time until the final state is achieved. This is also an example of the unidirection-
J1.8) Enlropyandthesecondlawoflhermodynamics 479

1 2 1 2
F igu re 11-11

ality of irreversible processes, because, as we see when we look at Fig. 11-11, if the gas is
initially in container I and by some means (such as removing the wall w) it is allowed to
expand freely into container 2, in a short time the molecules of the gas are distributed
over the combined volumes of I + 2. However, no one expects that at a certain later
time, as a result of the molecular motions, all molecules of the gas will appear concen­
trated back in container I. This process is possible but highly improbable. Thus the
free-expansion process V —> 2 V occurs in nature, but the reverse process does not. Ac­
cording to the second law of thermodynamics, the first must correspond to an increase in
entropy of the gas and the second to a decrease.
Let us now proceed to compute the change in entropy. The entropy of the gas in the
first state is

5 1 = k X In (v T 3/2) -F S 0.

Once equilibrium is re-established, and the volume is doubled, the entropy is

52 = kX In (2 vT3' 2) + S0-

The temperature has not varied because the average kinetic energy of the molecules of
the ideal gas has not changed. The molecules only move in a larger space. The change of
entropy in the process is therefore

S = S2 - S i = k X l n 2 > 0. (11.30)

So the (irreversible) process, which is one that certainly occurs in nature, produces an
increase in the entropy of the gas.
However, the reverse process, in which we assume that the gas initially occupies the
whole container (or volume 2V), and then at a certain later time occupies only the volume
V at the left, corresponds to a decrease in entropy; that is,

AS' = S i - S 2 = —k X In 2 < 0. (11.31)

Thus this process, although possible, is very unlikely to occur naturally if the gas is
isolated. It is true that we may compress the gas isothermally, reducing its volume from
2V to V, with a corresponding decrease in entropy equal to the value given by Eq. (11.31).
But this requires an external action, and it is then necessary to take the external changes
of entropy into account Io obtain the total change in entropy in the universe.
It is instructive to look at the same situation from a probabilistic point of view. From
definition (11.25), we have that

S2 - ,Si = k In P 2 - k In F 1 = k In γ
d80 Thermodynamics (11.9

When we compare this with Eq. (11.30), we have

P 2 _ „ 1V
In = JV In 2 = In 2N or
P1 " 2 '

In general, the number JV of molecules of the gas is very large and hence P 2 is much
greater than P\. This accounts for the rapid rate at which the gas expands freely up to
the volume 2V. For the reverse process, 2 V —> V, we get P 1/ P 2 = 2~N, and this is an
extremely small quantity for the number JV of molecules that are usually found in any
sample of gas. Hence it is extremely improbable (although possible) that at a certain
time all the gas molecules, as a result of their interactions, appear concentrated again in
the region V at the left. Of course, for a very small number of molecules (JV = I or 2,
for example), we have P 1/P 2 — i or and it is possible in a short time to observe “all”
the molecules (one or two) 011 the left-hand side. But then, of course, statistical methods
are unnecessary, and have no meaning, and it may be even possible to calculate the exact
times at which the particle or the two particles will be on one side or the other.

11.9 E n tro p y a nd H e a t
W e must now see how entropy is related to the other thermodynamic quantities
we have previously introduced. Suppose that a system in statistical equilibrium
undergoes an infinitesimal transformation as a result of its interaction with its
surroundings. T h e interaction results in a change o f the partition numbers n,- and
o f the possible energy states E i. Since U — ]T, UiE it we then have that

dU = Σ E i dm + Σ n <d E '· (11.32)

This equation holds whether the process is reversible or not. However, we shall
limit ourselves in this section only to reversible transformations, so that at each
instant the system is essentially in statistical equilibrium. The process must then
be slow enough so that at each instant the distribution o f the molecules can ad­
just to the corresponding m ost-probable partition.
Examining Eq. (11.32), we note that the first sum, E i dnit corresponds to a
change in internal energy due to a redistribution of the molecules am ong the
available energy levels, while the second sum, Σ · n, dE,, corresponds to a change
in internal energy' due to a change in the energy levels. Let us examine this second
term first. In Section 2.5 we discussed the stationary states of a particle in a one­
dimensional potential box of width a, and we found that the energy levels are
given by

2 ma 2

I f the width a is changed by the am ount da, the energy levels suffer a corresponding
change dEn, as indicated in Fig. 11-12. A similar change in the energy levels will
also happen in a 3-dimensional potential box of any shape. So, for the case of the
11.9) Entropy and heal 481

expansion of a gas, the change in energy }£,· n,- d/?,·

is due to the change in the dimensions or volume
of the container, and thus corresponds to what
we have called work. Recalling Eq. (11.14),
dU = dQ — dW , we conclude that the work done
by the system is

dW = ~ Y HidEi. (11.33)

Efiuation (11.33) gives the work done by the sys­

tem in terms of the change in the energy levels,
resulting, for example, from a change in volume.
This puts the statistical definition of the work Irfft':,
done by a system on a firmer basis than it was in
our preliminary definition, given in Section 11.3.
By introducing Eqs. (11.32) and (11.33) into
d U = dQ — dW , we conclude that we must write
AE2
K-,
dQ = Y E id n i (11.34) --- 1

for the heat absorbed by the system. That is,

the statistical quantity we have defined as heat is a Aa
a change in energy of the system due to molecular
Fig. 11- 12. Change in energy
jum ps between energy levels resulting from energy
levels of a potential box when
exchanges with the surroundings, a result in the width of the box is changed.
essential agreement with our previous definition
of heat in Section 11.4.
During a reversible process, there is an im portant relation between the change
in entropy, the heat absorbed, and the absolute temperature. This relation is

d S - f . for a reversible process only. (11.35)

I t is a direct consequence o f the definitions (11.25) for entropy and (11.34) for the
heat absorbed. The proof is given in Exam ple 11.6. Relation (11.35) indicates that
entropy is expressed in J ° K _ I or in cal ° K _ I , which was implicit in our definition
(11.25), in view of the units of k.
From E q. (11.35) we have dQ = T d S , which may be incorporated into
Eq. (11.14), giving, for a reversible process,

dU = TdS - dW . (11.36)

W hen only expansion work is done, the preceding relation becomes

dU = TdS - p dV, (11.37)

482 Thermodynamics ( 11.9

which expresses the change in internal energy during a reversible process in terms
o f the changes in entropy and volum e. Again we state that Eq. (11.14) is uni­
versally valid, while Eqs. (11.36) and (11.37) can be used only for reversible
processes.
From E q. (11.37), if the volum e is constant, d U v = T dSy or

It can be shown that, in general, P is an increasing function of the energy o f the

system ; that is, the larger the energy, the larger the partition probability P 1 so
long as the volum e remains the same. Hence, for such systems, the absolute tem ­
perature 7' is a positive quantity. Eor that reason T = O is called the absolute
zero, since in such cases there can be no temperature below that value.
H istorically, the concept of entropy was developed in physics in an order oppo­
site to that of our discussion. T h e convenience of the relation dQ /T for several
therm odynam ic calculations was recognized by K elvin, Clausius, and others dur­
ing the middle o f the nineteenth century. In 1865 Clausius introduced the name
entropy to designate a quantity whose change during a reversible process was given
by Eq. (11.35); that is, dS = dQ/T. T h e relation between entropy, as defined by
Clausius, and the probability o f a partition, as given b y Eq. (11.25), S — k In P 1
was first stated by Ludwig Boltzmann in 1877. Once the molecular approach to
thermodynamic processes was recognized as more fundamental, the Boltzmann
definition of entropy, instead of Clausius’ definition, became more relevant from
the theoretical point of view.

Note on the sipn of the absolute temperature

We may analyze the variation of the probability P with the total energy U at constant
volume in an intuitive way as follows: Suppose that the system of particles is enclosed
in a box of fixed volume. Then the possible energy levels are also fixed. Hence, if the
energy of the system is to be increased, some particles must be shifted from lower to
higher energy levels. Assume that, for a given total energy, the occupation numbers of
the partition are m , « 2, « 3, · · · , where « ι > «2 > «3 > · · - if the system is in equilib­
rium. Also assume, for simplicity, that 31 = 32 = 03 = · · · = L Then the probability
of this equilibrium partition is

P =
«il«2bt3l · · ·
Suppose now that the total energy U of the system is increased and that the energy in­
crease is accomplished by one particle shifting from level E i to level E 3. The probability
of the new partition is then
I
P' =
( « I — I ) !«21(713 + I) I · - ·
Therefore

P na+l
11.9) Enlropyandheal 6H3

If « ι is larger than «3 by at least 2 units (in general, m is much larger than 03 ), we have
that P ' is larger than P. Hence we conclude, in general, that P increases with the energy
U, at constant volume. Of course it is possible that under certain circumstances the
partition probability does not change, or it may even decrease when the total energy
increases. In particular, when the particles of a system have only a limited (or finite)
number of accessible states, it may be shown that P may be a decreasing function of the
energy for certain energy ranges. This would result in a negative absolute temperature
at such energies (see Problem 11.17).

E X A M P LE 11.6. Derivation of Eq. (11.35) for the relation between the change of en­
tropy and the heat absorbed by a system in a reversible transformation.
Solution: Let us suppose that our system obeys Maxwell-Boltzmann statistics, an
assumption of wide validity. Then the entropy for an equilibrium state is given by
Eq. (1 1.2S); that is,

S = Y + IcN ln | + fc :V .

For an infinitesimal reversible transformation in which the total number of particles

does not change,

d S -^dT+IcN y - (11.38)

since d(ln Z) = dZ/Z. Recalling the definition (10.22) for the partition function in
Maxwcll-Boltzmann statistics, Z = 2Z, gie~E>lkT, we have that

v-s dEi - E iIkT , V 1 Ei „ . - W r ,it

9* dT·
S »

Then, using Eq. (10.25), we may write

, dZ I N - E i Ik T . I N - E iIk T r
kX Y = ~ j i 2-, z<>ie dL< + f i L , z 9<e E‘ dT

(11.39)

To obtain the last result, we used Eqs. (10.2) and (11.33). Substituting Eq. (11.39) in
Eq. (11.38), we get

dU , d ll' dU+d\V
dS = Ύ + Ύ ~ = — r -------

Then, since from Eq. (11.14) we have dU + d ll' = dQ, we finally obtain

.ς dQ
"F 1

which is relation (11.35), relating the change in entropy and the heat absorbed. We
must keep in mind that Eq. (11.35) is valid only for a reversible process in view of the
fact that our derivation used the equilibrium partition function.
080 Thermodynamics (11.10

11.10 IHsrnssion o f I tTOfosHrs in T r r m s o f Enfrttpy

When a system passes from state I to state 2 by means of a reversible transforma­
tion, \vc have from Eq. (11.35) that

S2 - S 1 = f -Q (11.40)

gives the change in entropy. The integral on the right-hand side is independent of
the reversible transformation followed when the system goes from state I to state 2
because the entropy depends only on the state of the system. Aiso AS = S 2 — Si
depends only on the initial and final states, but not on the process.
In the case of an isothermal reversible transformation, T is constant and
E q . (11.40) becomes

C2
S2 - S 1 = y, J 1 dQ = Q or Q = 7’ (S 2 - S 1),

for isothermal processes only. (11.41)

T h us the change S 2 — S 1 is positive or negative depending on whether heat is

absorbed or rejected, since T is positive. For an adiabatic reversible transforma­
tion, since dQ„ = 0, Eq. (11.40) gives

,S2 — S 1 = 0 or S = const. (11.42)

T h us adiabatic reversible transformations are at constant entropy, and for that

reason they are also iscntropic. N ote, however, that an adiabatic irreversible
transformation is not necessarily isentropic.
From Eq. (11.3'>) we also have that

Q = JJ Td S (11.43)

gives the heat absorbed in going from state I to state 2 by a reversible transforma­
tion; this integral depends on the particular transformation. In fact , the reversible
transformation may be represented by a line in a diagram in which the ordinate
corresponds to the temperature T and tho abscissa to the entropy S, as in Fig. 11-13.
Then Q is the area under the curve from .S1 to S 2- If the transformation is a cycle
such as /1(1)Z?(2).4 (Fig. 11-14), we then have that the change in entropy is zero,
,S2 — ,S1 = 0, since we return to the initial state, and

AS = <d “ = 0, reversible cycle, (11.44)

while the net heat absorbed b y the system in the cycle is

Q = J t (/,S = area within t he cycle in (T , <S)-coordinates

= work done by the system during the cycle. (11.45)

11.10) Discussion of processes in terms of entropy 485

F ig . 11-13. D iagram ofareversiblepro- F ig . 11-14. Cycle. Theheatabsorbedby

cess in the T-S plane. The heat absorbed the system in describing the cycle clock-
during the process is given by the shaded wise is equal to the area enclosed by the
area. cycle in a T-S diagram.

This is a relation o f great im portance in therm odynam ic calculations. T h e student

should recognize that the entropy is a variable that may be used to describe a
process in the same way as pressure, volum e, or temperature.

E X A M PLE 11.7. Thermal efficiency of an engine operating in a Carnot cycle.

S olution: A Carnot cycle is a cycle composed of two isothermal and two adiabatic re­
versible transformations. No matter what the working substance is, it is represented by
the rectangle ABCD of Fig. 11-15, where AB and CD are the isothermal transformations
and BC and DA are the adiabatic or isentropic transformations. The cycle is described
in a clockwise fashion, as indicated by the arrows. Let us designate the temperatures of
the two isothermal processes by T i and T i, with T i larger than T 2 · During the isothermal
process A B at the higher temperature T i, the entropy increases and the system absorbs
an amount of heat Qi; during the isothermal process CD at the lower temperature T 2 ,
the entropy decreases and an amount of heat Q2 is rejected. During the two adiabatic
transformations the entropy remains constant and no heat is exchanged with the sur­
roundings. The changes in entropy during each
transformation, according to Eqs. (11.41) and I B
(11.42), are

ASab = Qi/Ti, isothermal, heat absorbed, Jg=Q

ASbc = 0, adiabatic,
AScd = — Q i/T 2 , isothermal, heat rejected, D C
ASda = 0, adiabatic.

The net change in entropy in the cycle is zero

and

.0 Qi Q2 n Qi Q2
ASwe,. = - - - = ° or - = - · S1 S2

F ig . 11-15. Carnot cycle in a T-S

(11.46) diagram.
086 Thermodynamics (.11.10

Tliis gives the relation between the heat absorbed and rejected and the corresponding
temperatures. Equation (11.46) holds for any substance that undergoes a Carnot cycle,
whether the substance is an ideal gas or not, since we have made no special assumption
about the internal structure of the substance. In the ease of a gas, the cycle is accom­
plished by a series of expansions and compressions.
The net heat absorbed by the system during the cycle is Q = Q i — Q >- This is also
equal to the work IF done by the system during the cycle. According to Eq. (11.45), we
may write
H' = Q = area of rectangle A B C D = (T i — T2)(S 2 — S i).

On the other hand,

Qi = Ti A S ab = Ti(S2 - Si).

Therefore the efficiency of a thermal engine operating according to a Carnot cycle (defined
as the ratio of the work done to the heat absorbed at the highest temperature, per cycle) is

„ Il- ( T 1 - T 2) ( S 2 - S i ) T i - T 2
h = Q r T 1(S2 - S i ) = ^ — ( l l -47)

Thus we see that Ihc efficiency o f a thermal engine operating according to a reversible Carnot
cycle is independent o f the working substance and depends only on the two operating tempera­
tures. This result is commonly known as Carnot's theorem.
Equation (11.47) also shows that the absolute temperature must be a positive quantity.
The reason for this is that if T2 were negative, then the thermal efficiency would be greater
than one (or > 1 0 0 % ), which is incompatible with the conservation of energy. Besides its
importance in the design of thermal engines, Carnot’s theorem shows that a reversible
thermal engine may be used as a thermometer. For this purpose it is necessary that the
engine operate between a standard temperature and the temperature to be determined.
By measuring the efficiency of the engine and applying Eq. (11.47), one can find the un­
known temperature.

EXAM PLE i l . 8 . Discussion of cooling by adiabatic demagnetization.

Solu tion : One of the most important techniques used to cool a substance down to
temperatures of the order of IO-3 °K is the method known as adiabatic demagnetization.
We shall give only a qualitative discussion, bringing out the physical ideas involved and
omitting in this instance the. detailed math­
ematical discussion.
The entropy of a substance increases with
temperature more or less as indicated by
curve (I) of Fig. 11-16. If the substance is
paramagnetic and a magnetic field is ap­
plied, it produces an ordering effect, tending
to orient the magnetic moments of the mol­
ecules along the direction of the magnetic
field. This results in a lowering of the en­
tropy, as indicated by curve (2) of Fig. 11-16,
since the action of a magnetic field brings
about a decrease in the disorder of the
molecules.
 Problems 487

Suppose now that the substance is initially in state .4 with no magnetic field present,
and that a magnetic field is applied isothermally. The substance undergoes the trans­
formation AU. Next we cut off the magnetic field adiabatically. Then if the process is
reversible, the entropy does not change and the system undergoes the transformation BC,
ending at point C of curve (I), corresponding to a temperature T 2 , much lower than the
initial temperature T i. If this process is repeated several times, a very low temperature
may be reached.

Kvffrent-oti

1. "The Microscopic Interpretation of Entropy,” I). Frisch, Am. J. Phys. 34, 1171 (1966)
2. “ Irreversibility in Simple Systems,” A. Hobson, Am. J. Phys. 34, 411 (1966)
3. “A Hundred Years of Entropy,” M. Dutta, Physics Today, January 1968, page 75
4. “Concepts of Classical Thermodynamics,” A. Buchdahl, Am. J. Phys. 28, 196 (1960)
5. Statistical Thermodynamics, E. Schrodinger. Cambridge: Cambridge University Press,
1964, Chapters 3, 4, and 5
6. Statistical Physics, G. Wannier. New York: John Wiley, 1966, Part I
7. Fundaynenlals of Statistical Thermodynayyiics, R. Sonntag and G. Van Wylen. New
York: John Wiley, 1966, Chapter 4
8. The Feynyyian Lectures on Physics, Volume I, R. Feynman, R. Leighton, and M. Sands.
Reading, Mass.: Addison-Wesley, 1963, Chapters 44, 45, and 46
9. A Source Book in Physics, W. Magie. Cambridge, Mass.: Harvard University Press;
page 220 (Carnot), page 228 (Clausius), page 236 (Kelvin), page 262 (Boltzmann)

K roblom n

11.1 A gas is maintained at a constant 11.3 When a system is taken from state
pressure of 20 atm while it expands from a A to state B along the path ACB (see
volume of 5 X IO" 3 m3 to a volume of Fig. 11-17), the system absorbs 80 J of
9 X IO-3 m3. What amount of energy heat and does 30 J of work, (a) Given that
must be supplied as heat to the gas: (a) to the work done is 10 J, how much heat
maintain its internal energy at a constant
value? (b) to increase its internal energy
P
by the same amount as the external work
done? Express your result in calories and
in joules.
11.2 A gas, initially at a pressure of 4 atm
and having a volume of 4 X IO-2 m3, ex­
pands so that the relation pV = const
holds. Under such circumstances the tem­
perature, and hence the internal energy,
of the gas remain the same. Calculate the O V
work done and the heat absorbed when the
volume is doubled. Figure 11-17
OHH Thermodynamics
is absorbed by the system along path
A DB? (b) The system is returned from
state B to state A along the curved path.
The work done on the system is 20 J.
Docs the system absorb or liberate heat,
and how much? (c) Given that U a = 0
and U d - 40 J, determine the heat ab­
sorbed in the processes A D and AB.
11.4 A gas undergoes the cycle shown in
Fig. 11-18. The cycle is repeated 100
times per minute. Determine the power
generated. The data are as follows: At A
the pressure p = 30 atm and the volume
V = 2 liters; at B the pressure is 10 atm
and the volume is 8 liters.
F ig u re 11—18
11.5 Plot the lines describing isochoric
transformations of an ideal gas for three
different volumes all on the same graph.
Repeat for isobaric transformations for
three different pressures and for isothermal
transformations for three different tem­
peratures.
11.6 Show that the work done by an ideal
gas during an isothermal expansion is
Wt = N R T ln V2/V i = Ν β ΓΙη p\/p2-
What amount of heat is absorbed during
the process? [Hint: Use Eq. (11.16).]
11.7 The heat capacity Cr of most sub­
stances (except at very low temperatures)
can be satisfactorily expressed by the
empirical formula
Cp = a + 2bT - cT ~ 2,
where a, b, and c arc constants and T is the
absolute temperature, (a) In terms of a, b,
and c, calculate the heat required to raise
the temperature of one mole of the sub­
stance at constant pressure from T i to TV
(b) Find the average heat capacity between
temperatures T i and TV (c) For magne­
sium, the numerical values of the constants
arc a = 25.7 X IO3, 6 = 3.13, and c =
3.27 X 10®, when Cr is in J 0K -1 mole- 1 .
Calculate the heat capacity of magnesium
at 300°K and the average heat capacity
between 200°K and 400°K.
11.8 The coefficient of cubical expansion
at constant pressure is defined as
β = ( I / V ) ( d V / d T ) ri
and the isothermal bulk modulus is defined
as
x = - ( l / V ) ( d V / d p ) T.
Prove that
(.θβ/3ρ)τ = ~ (d K / d T )r .
11.9 A gas composed of N molecules, at
temperature T , occupies a container of
volume Fi separated from an empty con­
tainer of volume V 2 by a removable parti­
tion. When the partition is removed, the
gas occupies the whole volume F i + V 2 ·
Show that (a) the temperature of the gas
remains the same and (b) the change in
entropy is AS = kN In ( I + F 2/ F 1). (c)
Verify that AS is positive.
11.10 Consider two samples of different
gases, designated a and b, both at the same
temperature T, composed of N r and Ni,
molecules, respectively, and occupying
adjoining containers of volumes Fi and
F 2, separated by a removable partition.
When the partition is removed and both
gases are mixed, we have N a molecules of
gas 0 and Nb molecules of gas b both
occupying the volume F i + F 2. Show
that (a) the temperature remains the same
and (b) the change in entropy is AS =
IcNa In ( I + V 2/ V 1) + kNb In ( I + F , / F 2).
(c) Verify that AS is positive.

11.11 Consider two samples of the same
gas, both at the same temperature T, com­
posed of N i and N 2 molecules, respectively,
and occupying adjoining containers of vol­
umes V I and V2, separated by a removable
partition. When the partition is removed,
we have a sample of the gas composed of
N i + N 2 molecules occupying the volume
Vi + V 2. Show that (a) the temperature
remains the same and (b) the change in
entropy is
(Ni + W 2) V i J
(V , + V 2W 2I
+ kN 2 In
(Ni + W 2J V 2J
(c) Show also that if the two gases were
initially also at the same pressure, the
change in entropy would be zero. Why?
11.12 The llelmholtz free energy is defined
as F = U — TS. Show that
F k N T [In ( Z / N ) + I).
Find F for an ideal gas. Also show that the
parameter a defined in Eq. (10.11) is equal
to -F / k N T .
11.13 Referring to the system described
in Problem 10.33, show that (a) the heat
capacity of the system can be written as
C, = Cr.tr + Cr.im, and (b) the entropy of
the system can be written as S = Str+ Sint,
where
S,r = ^ γ + k N l a ^ + k N ,
U i„t
S in t — + kN In
iis applies, for example, to the computa-
m of the heat capacity of a paramagnetic
s placed in a magnetic field, with
11.14 A system is composed of particles
whose internal degrees of freedom corre­
spond to states of energy 0, e, 2e, . . . , ne,
Problems 489
. . . , where n varies from zero to infinity.
Find the entropy and the heat capacity
due to the internal degrees of freedom of
the system. [Hint: Refer to Problems 10.6
and 11.13.]
11.15 A system is composed of particles
that, due to their internal degrees of free­
dom, can exist only in either of two states,
of energy —t and + « , in addition to the
translational kinetic energy of the parti­
cles. Find the entropy and the heat capac­
ity (at constant volume) of the system due
to the internal degrees of freedom of the
particles, as a function of the temperature
of the system. Plot both quantities as a
function of the absolute temperature of
the system. [Hint: See Problem 11.13.]
Apply your result to calculate the magnetic
entropy and the magnetic heat capacity of
electrons in a magnetic field.
11.16 A system composed of N molecules,
each having an angular momentum j and a
gyromagnetic ratio g, is placed in a mag­
netic field (B. Show that the entropy due
to the magnetic field when equilibrium is
reached is
Sm = —kNjx [ ( l + coth (j +
]■
- l .2cj o t h l2r + l n 8> h.(i
sinh
t * )g'
£1
where x = gynQA/kT. Also calculate the
heat capacity at constant volume.
11.17 The number of particles in a system
is N . The particles can only be in cither of
two states with energy -(- t or —t, but the
particles do not have any translational
kinetic energy. Given that the total
energy of the system is U, show that the
absolute temperature is given by
I k N - U/t
T 2e N +U /e'
Verify that the absolute temperature is
positive (negative) if U is negative (posi­
tive).This situation applies, for example,
to a set of particles (electrons) of spin §
490 Thermmlynamics
when they are placed in a magnetic field
and only the spin-magnetic interaction
energy is considered. [Ilin t: First show
that
In P = N In 2 - £(A + U/t) In (V + U/t)
- i(.V - U/t) In (N - U /t);
then plot In P as a function of U.
that U varies from —Mt to .Vt.]
11.18 Oxygen molecules have a spin of I,
so that oxygen is a paramagnetic gas.
Determine the spin partition function of
oxygen placed in a magnetic field ffi. Ob­
tain the energy of the gas, its average
magnetic moment, its spin entropy, and
its heat capacity at constant volume due
to the magnetic field.
11.19 Show that the change in entropy
of a substance heated rcversibly at con­
stant pressure (assuming that the specific
heat remains constant) is
S2 - S 1 = NC p In ( T 2ZT1).
Apply your result to I kg of water heated
from room temperature (298°K) up to its
normal boiling point (373°K).
11.20 When a substance undergoes a
change of phase (fusion, vaporization,
sublimation, etc., or the reverse), heat is
absorbed (or liberated) at constant tem­
perature. For water the heat of fusion is
1440 cal mole-1 and the heat of vaporiza­
tion is 9720 cal mole-1 . Calculate the
change in entropy of one mole of water,
given that it is heated rcversibly from
—20°C to 150°C at a constant pressure of
I atm. The heat capacity of ice is 9.0 cal
0K -1 mole-1 and the heat capacity of
steam at constant pressure is 8.6 cal 0K -1
mole- 1 .
11.21 If i is a function of the variables x
and y, then
άξ = (Of/dx)ud x + (d£/dy)t dy.
Then recognize that from Kq. (11.37) we
have that
T = (dU/dS)v
and
p = ~ (d U / d V )s.
Write the corresponding expressions de­
rived by differentiating: (a) H = U + pV,
(b) F = U - TS (called the Helmholtz
Note
free energy), and (c) G = U + pV — TS
(called the Gibbs free energy).
11.22 If ί/ξ = Λ ' ώ + Ydy is an exact
differential so that .Y = (d(/dx)„ and
Y = (d£/dy)x, we have that (dX/dy)x =
(dY/dx)u. Given the thermodynamic func­
tions (a) U, (b) H = U + pV, (c) F =
U - TS, and (d) G = U + pV — TS,
determine the relations, of the type stated,
that are derived from them; these are
called the Maxwell relations. [Hint: See
the preceding problem.)
11.23 Some thermodynamical quantities
are proportional to the number of particles
(or to the mass of the system) and others
are independent of the number of particles.
The first type of quantities are called exten­
sive and the second type are called intensive.
Determine which of the following quanti­
ties are extensive and which are intensive:
U, IF, Q, p, V, T, S, II, (dH/dph,
(dH/dS)p, Cp, Cv, F = U - T S1 and
G = U + p V - TS.
11.24 Show that Cp - C v = S2TVfaK.
[Hint: First express dS in terms of dT and
dV. Then show that
(dU/dV)T + p = T(dp/dT)v.
For the definition of β and k , see Prob­
lem 11.8 .)
11.25 Given that p is the pressure at
which a substance exists in two phases in
equilibrium at temperature T , and V i and
V 2 are the volumes of I mole of the sub­
stance in each phase, show that
L - T ( A ) i Vt - V , ) .

where L is the molar lieat of change of
phase; i.e., the heat absorbed when I mole
passes from one phase to the other. This
expression is called Clapcyron’s equation.
[Hint: Use the relation
(dS/dV)T = Op/dT)v,
derived in Problem I 1.22.)
11.26 One mole of an ideal gas at 25°C
and I atm is heated at constant pressure
until its volume is tripled. Calculate
(a) AU, (b) W, (c) Q, (d) AS, (c) AU, (f) AF,
(g) AG. (See Problem 11.21 for the defini­
tions of F and G.)
11.27 Compute the change in entropy,
enthalpy, and internal energy of I mole of
water when it melts at a temperature of
O0C and a pressure of I atm. The density
of ice is 0.9 X IOi kg m -3 and that of
water is 1.0 X 10:! kg m- 3 . The heat of
fusion of water is 1440 cal mole- 1 .
11.28 (a) One kilogram of water at 0°C is
brought into contact with a large body at
IOO0C. When the water has reached IOO0C,
what has been the change in entropy of
the water? Of the body? Of the universe?
(b) If the water had been heated from 0°C
to IOO0C by first bringing it in contact
with a large body at 50°C and then with
a large body at IOO0C, what would have
been the change in entropy of the water
and of the universe? (c) Explain how the
water might be heated from 0°C to IOO0C
with no change in the entropy of the
universe.
11.29 A body of heat capacity C1,i and
containing Ni moles at temperature T i is
placed in thermal contact with another
body of heat capacity C1,2 and containing
N2 moles at temperature T 2 . The only
process that can occur is a heat exchange.
Is the process reversible or irreversible?
(a) Show that when thermal equilibrium
is reached the common temperature is
γ _ NlCylTl + N’^Cp-zTo
NlCpl + N2CP2
Problems 491
Verify that T is a temperature that falls
between T i and Τ·>. (b) Show that the
total change in entropy is
T T
AS = NiCpi In — b N2Cp2 In = - ·
Ji 12
Also verify that AS is positive. [Ilin t: For
the last question, assume that T \ is smaller
than T > so that the three temperatures are
in the order T i < T < T>. Then add and
subtract from the above expression for AS
the quantity N2Cp2 In {T/T\).[
11.30 Assume that 100 g of water at 90°C
is jiourcd into a 0.3-kg aluminum container
initially at room temjierature (25°C).
Calculate the change in entropy of the
aluminum, of the water, and of the entire
system after thermal equilibrium has been
reached. Is the Jirocess reversible or
irreversible?
11.31 A liquid at a temperature T i is
mixed with an equal amount of the same
liquid at a temperature T 2 · The system
is thermally insulated. Show that the en-
tropy change of the universe is
ΛC n /-. I T I T 2
AS = 2.\Cp In — —- >
2\/ T i T 2
and prove that this is necessarily positive.
11.32 Compute 1Γ, Q, AU, AU, and AS
when I mole of steam at IOO0C is con­
densed by isothermal comjiression at a
pressure of I atm. The heat of vajioriza-
tion of water is 9720 cal mole-1 and the
density of steam in such conditions is
1.686 kg m - 3 .
11.33 One liter of an ideal gas at 300°K
and at a pressure of 15 atm expands
isothermally until its volume is 10 liters.
Comjiute 1Γ, Q, AU, AU, and AS.
11.34 One mole of nitrobenzene
(C eH 5N O 2)
is vajiorizcd at 210°C and a pressure of
I atm. The heat of vaporization is 9730
49 2 Thermodynamics

cal mole- 1 . Compute (a) Q, (b) W, (c) AU,
(d) AU, (e) AS, (f) ΔΕ, and (g) AG.
11.35 The energy density E of blackbody
radiation is a function of the temperature
alone (remember Eq. 1.8). Also the pres­
sure exerted by isotropic radiation on a
perfectly absorbing surface is Je'. By
means of Eq. (11.37), show that e is pro­
portional to T 4, which is the Stefan-
Boltzmann law (Example 1.4). [Hint:
Write U = kV in Eq. (11.37) and note that
dv. - (de/dT) dT\ then apply the proper­
ties of an exact differential, as used in
Problem 11.21.]
11.36 Show that, for a reversible cycle in
which only expansion work is done,
Note the similarity of this equation to
Eq. (11.44).
 12
THERM AL PROPERTIES
OF GASES

12.1 Introduction
12.2 The Equation o f Stale o f an Ideal Gas
12.3 Equation o f Stale fo r Real Ga
12A Heat Capacity o f an Ideal M ona iom ic Gas
12.5 IIeat Capacities o f an Ideal Polyatom ic Gas
12.6 The P rin c ip le o f E qu ip a rtition o f Energy
//94 Thermal properties of gases ( 12.2

12.1 In tro d u c tio n •

In the tw o preceding chapters we have laid the groundwork for a discussion of
the general properties of m atter in bulk: the mechanical, electrical, thermal, and
chemical properties of matter or large aggregates o f atoms or molecules. VVc can
approach the discussion of these properties from tw o opposite directions. The
experimental approach calls for extensive laboratory measurement and tabulation
o f properties such as density, specific heat, thermal and electrical conductivities,
viscosity, elastic moduli, surface tension, thermal expansion, chemical reaction
rates, etc., and the empirical dependence o f these quantities on external factors
such as pressure and temperature, applied electric and magnetic fields, etc. This
has been the traditional procedure for those interested primarily in a knowledge
o f these properties for specific applications. T h e alternative approach is theoretical·,
this approach consists in an evaluation o f the bulk properties of m atter in terms
of the atom ic and molecular structure and in terms of the interactions between
atoms and molecules. Although these interactions are essentially electromagnetic,
some sim plifying assumptions o f a largely phenomenological nature are made
(such as a reasonable intermolecular potential energy). Because of the large num­
ber of particles involved, the theoretical approach requires the use of statistical
methods.
In this chapter we shall illustrate the theoretical procedure by working out some
representative problems related to the thermal properties of gases. T h e extension
of t he methods of this chapter to other states of matter or to special topics belongs
to engineering, physical chemistry, and applied physics, and will not be discussed
in this text.

12.2 T h e E q u a tio n o f State o f an Id e a l Hatt

T h e simplest of all systems of particles is an ideal gas, and in this section we shall
obtain its equation o f state. In Exam ple 11.6 we derived Eq. (11.39), that is,

. ... dZ SW U /in I \
kN γ = — γ 2 ά'Γ. (12.1)

This equation relates the change in the partition function to thework done by a
system and its change in temperature. F or the case of a gas, in which the only
w ork is expansion work, we have (tW = p dV. Also d (ln Z ) = dZ/Z. T h us we
m ay rewrite Eq. (12.1) in the form

> »r ,/I V dV , U d T
k N d(ln / ) = - ψ - + - ψ ϊ - ■

If the temperature is constant, d T = 0, and solving for p, we have

( 12.2 )
 The equation of stale of an ideal gas 'i95

where the subscript T indicates that the tem perature is constant. Equation (12.2)
relates the pressure of a system to its temperature T, its volum e V , and the internal
structure of the system, as expressed by Z. Therefore it provides a relation of the
form f(p , V , T ) = 0. Hence we may call E q. (12.2) the equation of stale of the
system.
For an ideal gas, the partition function is given by Eq. (10.40),

(12.3)

which, when substituted in Eq. (12.2), gives

kNT . „ .
V = y~ ' (12.4)

Equation (12.4) is the equation of state of an ideal <jas. It is som etim es written as

pV = kNT, (12.5)

or, since R = k N \ = k N /n, where N = N / N \ is the number of moles o f the

gas and N \ is A vogadro’s number,

pV = N RT. (12.6)

W e can derive this equation in other, perhaps m ore direct, ways. In one case, we
can com pute the pressure of the gas by analyzing the change in mom entum of
the gas molecules when they hit the walls of the container. In another method, we
can use the virial theorem to show that Eq. (12.5) gives the pressure o f a gas when
the intermolecular forces are neglected.* T h e fact that we arrive at the same
result in all derivations shows the consistency of our methods.

Note on the measurement o f temperature. In Section 10.4 we associated the temper­

ature of a system of particles with the average energy of a particle. In Eq. (10.41),
which is Pit. = %kT, we were more specific about the relation between the temperature
of an ideal gas and the average kinetic energy of the gas molecules. However, we must
now consider two important aspects: First, in the defining equation (10.23), we intro­
duced two new quantities, T (the absolute temperature) and k (Boltzmann’s constant),
and we must decide how they can be measured independently. Second, all human beings
have an intuitive concept of temperature based on sensorial experience, as reflected by
our feelings of hot and cold. We are all accustomed to measuring temperature in terms
of a number given by a device called a thermometer. Therefore we must correlate our
statistical definition of temperature with this intuitive notion.
Let us consider a mass M of a gas containing N molecules. If we neglect the effect of
the intermolecular forces, the equation of state is given by Eq. (12.5); that is, pV = kNT.

*See, for example, Fundamental University Physics, Volume I, Section 9.13 and Exam­
ple 9.16.
 ■456 Thermal properties o f gases (12.2

Suppose that we bring the gas into thermal equilibrium with some other physical system,
which we assume may be kept at a fixed temperature. This system may be an equilib­
rium mixture of water and ice at the standard pressure of I atm. This is called the normal
. freezing point of water. We measure the pressure and the volume of the gas at this fixed
temperature, and obtain the values po and To, respectively. Next we decide to assign a
convenient (but arbitrary) value To to the fixed temperature, which is also the tempera­
ture of the gas. Therefore we may write poVo = kNTo. This automatically fixes the
value of the Boltzmann constant, k = poVo/NTo, since we can obtain N if we know
the mass of each molecule.
To determine the temperature of the gas when its pressure is p and its volume is V ,
so that pV = kN T, we simply eliminate the factor kN, using the standard values, and
obtain
T = ToipV/poVo),

which gives T in terms of our standard reference temperature To and other measurable
quantities. In this way our mass of gas has become a gas thermometer. If the volume of
the gas is maintained constant and equal to Vo, we have T = Toip/po), resulting in a
constant-volume gas thermometer. We may use other substances as thermometers instead
of gases, such as liquids or metals whose dimensions (volume or length) change with the
temperature. Other thermometers use electric conductors (such as platinum wires)
whose resistance varies with the temperature. Since the equation of state of these sub­
stances is more complicated, in practice we calibrate these thermometers against a gas
thermometer. In this case the thermometer agrees with the gas thermometer only at
the calibration points. Since the property chosen may not vary linearly with the gas
temperature, there may be slight discrepancies at intermediate temperatures.
We may choose the value of To on the basis of several points of view. For example, we
may choose another process which conceivably occurs at a fixed temperature, such as
water boiling at the standard pressure of I atm, which is called the normal boiling point
of water. Then we may decide that the temperature of this second reference point is
100 units, or degrees, above To, chosen as the normal freezing point of water. Given that
pi and F j are the pressure and volume of the gas at this new temperature, we have that
P iF i = k N (T o -l· 100). Solving for kN from the equation poFo = kNTo and substi­
tuting this value in the above equation, we find that

To = 100poFo/(piFi — poFo),

from which we can obtain a numerical value for To in this arbitrarily chosen scale. The
value obtained for To as a result of this type of experiment (and many other experiments
using different techniques) is To = 273.15. Each of the units is called a degree Kelvin,
designated by °K. Nowadays it is preferred to simply assign, by definition, the value
To = 273.15 °K to the temperature of the normal freezing point of water. The value of
the Boltzmann constant then becomes k = 1.3805 X IO-23 J 0K -1 .
It is important to realize that the technique we have explained for measuring tempera­
ture is based on the ideal gas approximation. If we use different gases, the results ob­
tained will not be the same because the effect of the intermolecular forces, as it appears in
Eq. (12.7) of the next section, is different for each gas. Usually hydrogen or helium is
used. It is most desirable to have a temperature scale independent of the substance
being used as a measuring medium. We can accomplish this by using a reversible thermal
engine operating in a Carnot cycle (see Example 11.7). Then the efficiency of the engine
12.3) Equation of slate fo r real gases 1*97

is independent of the substance used in the engine, and is given by Eq. (11.47), E =
(T i — T f )/ T i. Given that T 2 is our standard temperature To and T i is the tempera­
ture T to be measured, vve Iiave

p T1 - T 0
~~ T

Hence if we measure E, we obtain T. It has been found experimentally that for a thermal
engine operating between the normal boiling and freezing points of water, E = 100/373.
If we choose T — To = 100 degrees for those two temperatures, we again have that
To = 273°K. The temperature obtained using a reversible engine is called the thermo­
dynamic temperature. This method was proposed by Kelvin. Both Kelvin and Joule
made careful experiments comparing the temperature measured by a constant-volume
hydrogen thermometer with the thermodynamic temperature.

12.3 E q u a tion o f State fo r Ite a l Gaoen

W h e n w e are d e a lin g w ith re a l gases, w e m u st ta k e in to a c c o u n t th e in te rm o le c u la r
forces a n d th e fin ite d im en sio n o f th e m olecu les. T h e in te rm o le c u la r fo rce s are o f
fa ir ly s h o rt ra n g e an d d ecrea se r a p id ly w ith th e d ista n ce b e tw e e n m olecu les. T h e r e ­
fo r e th e p ressu re o f a re a l gas w ill b e closer t o th e id e a l gas v a lu e , E q . ( 12.4 ), th e
la rg e r th e v o lu m e p e r m o le c u le ; i.e., th e la r g e r F / n . T h is su ggests th a t w e exp ress
th e p ressu re o f a re a l ga s in te rm s o f th e series

RT N2 A N3 B , N 4C ,
V = — + ^ γ ϊ + - γ ΐ + -γΤ + ··· ( 12-7 )

in n e g a tiv e p o w ers o f F /n . W e can c o n s id e r E q . (12.7) as the equation of state of a

real gas. A , B, C, . . . are q u a n titie s c h a ra c te ris tic o f each gas, c a lle d th e secon d ,
th ird , e tc ., virial coefficients. T h e y are fu n c tio n s o f th e te m p e ra tu re , an d d ep en d
on th e s tre n g th o f th e in te rm o le c u la r forces. B y m e a s u rin g p a t d iffe r e n t te m p e r a ­
tu res a n d v o lu m e s , w e can o b ta in th e v ir ia l c o e ffic ie n ts A ( T ) , B (T ), . . . e x p e rim e n ­
ta lly . H o w e v e r , to fin d a clu e to th e c o rre la tio n b e tw e e n th e v ir ia l co e ffic ien ts an d
th e in te rm o le c u la r forces, w e m u st o b ta in c e rta in th e o re tic a l re la tion s . O n e possi­
b ilit y is t o use th e virial theorem, w h ic h is d e r iv e d in m ech a n ics t e x ts .* T h is
th e o rem , w h e n a p p lie d to a gas, b eco m es

pV = N S T + I F ij · γ ,Λ . ( 12.8 )

'p a ir s / ave

w h e re F tj is th e fo r c e on m o le cu le i d u e to m o le c u le j, r ,7 is th e p o s itio n v e c t o r o f
m o le cu le i r e la t iv e to m o le cu le j , an d th e s u m m a tio n e x ten d s o v e r a ll p airs o f
m o lecu les. W h e n w e c o m p a re E q . ( 12.8 ) w it h E q . ( 12.7 ), w e fin d th a t

s(Σ 'p a ir s ' ave

= ν(^ + τ γ + τ ?+···)’ (12'9)
*See, for example, Fundamental University Physics, Volume I, Section 9.12.
498 Thermal properties of gases {12.3

which in principle allows us to correlate the virial coefficients A 1B 1C , . . . with the

intermolecular forces. T h e methods of statistical mechanics allow a more straight­
forward calculation of the virial coefficients, as we shall presently sec. However,
because the statistical mechanics o f systems com posed of interacting particles is
slightly m ore com plex than that o f systems of noninteracting particles, we shall
have to om it som e derivations.
Let us introduce the quantity Z = Z n /N called the grand partition function
o f a system o f noninteracting particles. Then, noting that

In Z = In {Z N/ N !) = N \ n Z - In .V!,

we may also write the equation of state ( 12.2) in the form

d
p = kT (I» Z ) ( 12 .10 )
dV

T or an ideal gas, using Eq. (12.3), we have

V (2 T m k T f 12Y f
Z jd r a l \r. ( 12. 11)
uas . IV

W hen we are considering real gases and therefore dealing with interacting mol­
ecules, wc have to extend the methods o f statistical mechanics explained in C hap­
ter 10 to include the internal potential energy E p = Σ α ιι pairs Epij- W e cannot go
into the mathematical details o f this extension; it is sufficient to indicate that, in
the case o f a real gas, the grand partition function Z has the form

2 = F [ ( 2 7 Γ 'ΐ Γ ) 3 ~ ' ] Λ / / · · · / e ~ E p ' k T d V ' d V 2 ' " ( l V s ( 1 2 1 2 )

A l l molecules

where the N volum e integrals correspond to-on e for each molecule. T h is appar­
ently formidable expression is, in fact, a very simple extension o f the partition
function for an ideal gas, because for an ideal gas we must make E p = 0 and then
e~ Ep' — I. Thus the multiple integral becom es

JJ- ■■J dVi dV2 ■■■dVit = V- V ■ V ■ ■ ■ = F v (12.13)

A l l molecules

since each molecule may be found throughout the entire available volum e. Then
Eq. (12.12) becom es
I '.V
I (2 irm k T )312 •v T -V _ L V C lirm k T )3' 2'
:V ! IV NI IV

in a g re e m e n t wi t h E q . ( 12. 11).
N o w , re tu rn in g to E q . ( 12. 12) , w e m u st w r ite th e p o te n tia l e n e rg y as

Ep = ^ h p ij
AU
pairs
 Equalion of stale for real gases 499

and use a reasonable expression for the intermolecular potential energy. Once we
know E v , we may in principle evaluate Z. B y applying Eq. (Γ2.10), we can obtain
the pressure p and expand the result in inverse powers of the volum e V . In this
w ay we can establish a relation between the intermolecular potential E pij and the
virial coefficients A t B , . . . Since we can determine the virial coefficients A 1B 1. . .
experimentally, this provides a very useful guide for investigating the form of
the intermolecular potential E v tj on a sort of trial-and-error basis until we can
calculate the correct virial coefficients. W e shall illustrate some of these techniques
in the remainder of this section.
Let us consider the multiple integral of kpij(r)
Eq. (12.12); that is,

/= //■ ·■ / e - B' lk T d V 1d V 2 ---d V .v ,

AU m olecules

where the summation

Ev = J2 E v ij
AU
pai rs

contains % N (N — I) terms, which is the

total number of different pairs of mole­
cules. N oting that

c(x + p + r - > = e* . ev . e* . . . t

we have that

, - B r IkT = J J e- £ W * r

AU
Fig. 12-1. Intermolecular potential
p a ir s energy.

where the sym bol Π means the product of all terms appearing. Also when E pij is
very small, the exponential factor is practically I. B u t (except when the molecules
are rather close) E pij is very small, due to the short range of the intermolecular
forces (see Fig. 12-1). Thus, using the expansion e ~ z = I — x + i-r2 — · · · , we
can write
- B fijlkT = ! _ E g j + I . . . = l + fih (l2 U )

and the quantity Jij is very small except when the tw o molecules are very close.
Therefore
e- B PikT = j j (1 + = i + χ ; /,■ > + ·■ ■
A ll AU
p a ir s p a irs

The terms that have been om itted involve products of 2, 3, . . . /,· /s, and we shall
neglect them, although, in a more detailed theory, they must be considered. W ith
500 Thermal properties of gases (12.3

this approxim ation we m ay write the integral I as

1 = / / ■ · · / (1 + Σ / « + · · ■ ) d V > d V * ■ ■ ■dyX-
AU AU
p airs
m olecules

T h e term having the factor I obviously gives F'v after integration, in agreement
with the previous result for an ideal gas in Eq. fl2 .1 3 ). Succeeding terms then
give the contribution of the intermolecular forces. T h e % N (N — I ) terms of the
summ ation are all alike, because Jij has the same form for all pairs of molecules.
Thus we m ay write their contribution in the form

iN (N - i ) v N ~ 2 J I j 12 d V j d v 2, (12.15)

where we have chosen the pair o f molecules I and 2 and the factor V N ~ 2 results
from the volum e integral for the remaining N — 2 molecules. In evaluating the
double integral, we may first choose our origin o f coordinates at molecule I to
perform the integral over d V 2 (Fig. 12-2). Designating the distance between I and
2 by r, we may then write
Z2

I j h * (r ) dV x dV2

= J { I 2 /12 M iITrr2 drJ dV j

where we have used d V 2 = 4irr2 dr for the

volum e element, because of the spherical
sym m etry of the problem. T h e integral

β = [ f i i ( r ) 4 v r 2 dr (12.16)
Jo

is independent o f the position of molecule I (so long as it is not close to the walls
of the container), and therefore

I I J u (T ) d V j dV2 = I β d V 1 = β f d V i = fiV.

Replacing ^ ( A r — I) by I N 2, which is a valid approximation when N is very

large, we then have Eq. (12.15) in the form %Ν2ν Ν ~ 'β , and we m ay write the
integral I as

/ = F-v + I N 2V " - ' β = V n ( l +

H ow ever, if successive terms are taken into account in the expansion of e EPlkrl
the result one obtains for I is
12.3) Equation of stale for real gases 501

The previous result is just the first tw o terms in the binomial expansion o f the
above expression. T h e grand partition function of the real gas, E q. (12.12), is now
given by the expression

up to the first order of approximation. This must be com pared with Eq. (12.11)
for a real gas. The last factor in Eq. (12.17) is the contribution of the intermolecular
forces to the grand partition function.
T o obtain the equation of state of a real gas, we now use Eq. (12.10). From the
expression (12.17) for Z, we have

In Z = N In V + N \n ( l + + F (T ),

where we have included in F ( T ) the remaining terms that are either constant or
depend on the temperature and do not affect the derivative in Eq. (12.10). W e
now approxim ate the second term, using In (I + x ) ~ x under the assumption
that x (= Ν β / 2 V ) is small compared with I (the quantity Nf3 /2 F is o f the order
of K T 4 at S T P ). Thus

In Z = N In V + ^ + F (T ).

Therefore

Γ0 J N N 2)3
LaF( 2^J7. V 2F2

which, substituted in Eq. (12.10), gives

_ . \N N 2βI f c J V T IcT N 2t3

P [V 2 V 2\ V 2V2 '

B ut remembering that N — NjVa and R = k N A, we m ay write

NR T K2R T n Αβ
V — y 2V2 ’ (12.18)

which is the resulting equation of state o f the real gas expressed in virial form, to
the first order of approximation. W e n o te th a t in Eq. (12.18) we have obtained only
tw o terms; this is a result o f the type o f the approxim ation which we have made
in the evaluation of Z. W hen we take these terms into account, the com plete
virial expansion results. Com paring Eq. (12.18) with Eq. (12.7), we see that the
second virial coefficient in our approximation is

A (T ) = -iR T N r f, (12.19)
502 Thermal properties of gases (12.3

which directly relates the intermolecular interaction (identified by /3) and the
virial coefficient A ( T ) (determined experim entally). This is tlje connection be­
tween the intermolecular interaction and the virial coefficients that we indicated
before.
W e shall not pursue our discussion any further; what we have said is enough to
indicate the method o f attacking the problem o f the equation o f state o f a real
gas, and in general o f any system com posed of interacting molecules. T h e case for
liquids and solids is more com plex, and we shall not discuss it in this text.

E X A M P L E 12.1. Evaluate the second virial coefficient for the case of a gas composed
of noninteracting hard spheres of radius ro-
Solution: This is a rather “ unrealistic” real gas because no intermolecular forces are
assumed until the centers of the molecules are a distance 2ro apart, at which time a
strong repulsion sets in. Thus the intermolecular potential energy is E pn = O forr > 2ro
and Ep12 = » for r < 2ro, resulting in /12 = 0 for r > 2r0 and /12 = — I for r < 2ro.
This “hard-core” potential, as it is usually called, is represented in Fig. 12-3. We have
called this an unrealistic potential energy because it cannot produce condensation, since
it has no minimum and therefore no stable separation between the molecules. However,
it does give us a simple model with which to check our physical ideas without undue
mathematical complications. Introducing the values of /12 in E q . (12.16), we obtain

When we substitute this value in Eq. (12.19), the second virial coefficient becomes

where b = N is four times the volume of the molecules in one mole. Hence
the equation of state of a gas composed of hard spheres, to the first-order approximation,
is
NR T Vt1RTb
τ/ ' I ro.

E X A M P L E 12.2. Extend the results of the previous example, to the case in which the
intermolcculai forces are attractive but very weak, except for r < 2ro, where a very
strong repulsion sets in, making the molecules almost like impenetrable hard spheres.

Solution: As a logical extension of the calculation performed in the previous example,

we may introduce rather weak but attractive intermolecular forces for r > 2ro, as illus­
trated in Fig. 12-4. Then we may continue with the assumption that /,7 = — I for
r < 2ro. But from Eq. (12.14), if E Pij/kT is small compared with unity, we may write
f i 2 = — Epi 2/kT for r > 2ro. Therefore Eq. (12.16) gives

r 2r0 /*oo 3

0 = Jo (— 1)4Tr2 d r + J 2 ( —Ep\2/kT)4rr2 dr = — + ■— >

12.3) Equation of state fo r real gases 503

EpU Epn- * Epi2

Fig. 12-3. Hard-core intermolecular po­ Fig. 12-4. Intermolecular potential

tential energy. No attraction at any energy with a hard core and weakly attrac­
distance. t i v e at larger distances.

where

« = f ( — E pi2)iirr 2dr
J2ra

is a positive quantity, since Ep12 is negative (sec Fig. 12-4) for r > 2ro- Substituting in
Eq. (12.19), using our previous definition of 6 and setting a = %N\a, we obtain .A =
RTb — a for the second virial coefficient. The equation of state, to the first order of
approximation, is then, using Eq. (12.7),

( 12.20)

This equation is satisfied with fairly good accuracy by many real gases, especially for
large values of F / n . The coefficients a and 6 are called van der IFaafs constants. They
are given in Table 12-1 for several real gases.

T A B L E 12-1 V an der W a aIs C o n stan ts

a, b,
Substance
N m4 kg-2 mole-2 m3 kg-1 mole 1

Helium 3.446 X IO3 0.02370

Hydrogen 24.68 0.02661
Neon 21.28 0.01709
Nitrogen 140.4 0.03913
Oxygen 137.4 0.03183
Ammonia 421.2 0.03707
Carbon dioxide 362.8 0.04267
Sulfur dioxide 678.1 0.05636
Water 551.9 0.03049
504 Thermal properties of gases ( /2.4

12. i Mleat Ca pa city o f aa Mdoai M o n a to m ic Mmati

In Section 11.7 we defined the heat capacities of a substance at. constant volume
and at constant pressure as

c'=Ks?),' (1221)
where 11 = U + p V is the enthalpy of the substance. In addition to their im ­
portance as coefficients in several practical calculations, the theoretical calculation
of the heat capacities o f a substance affords a means o f verifying the correctness
o f the model chosen to describe the substance. In this section we shall calculate
the heat capacities of an ideal gas, and by comparing these with the observed
values for real gases, we shall be able to conclude to what extent the ideal-gas
model is a good approximation.
Let us first consider an ideal m onatom ic gas. T h e internalenergy of such a
gas is purely translational kinetic energy, and isgiven by U = % xR T. Using
Eq. (12.21), we obtain

C r = §R = 12.4715 J m ole-1 0K -1
= 2.9807 cal m ole-1 0C - 1 . ( 12.22)

Taking into account Eq. (12.6) {p V = NR T ), we have that the enthalpy of an

ideal gas is

H = U + pV = f x RT.

Thus Eq. (12.21) gives

Cp = f R = 20.7858 J m ole- 1 0K -1
= 4.9678 cal m ole-1 0C - 1 . (12.23)

Therefore all ideal m onatom ic gases have the same heat capacities, independent
of the structure of the atoms. W e may note, from the above results, that

Cp - C v = R, (12-24)

so that Cp is larger than C r by the am ount R. T h e reason for this is that Cy is

related only to the change in internal energy, while Cp includes, in addition, the
expansion work of the gas when its temperature increases I degree at constant
pressure. It is simple to verify that this w ork is exactly equal to R. W hen the
pressure of the gas is constant, p dV = NR dT, and if the increase of temperature
is one degree, the work done is

IFp = J pd V = JJ +1 N R d T = N R.

Hence the work per mole done by the gas is R. From this proof we see that
Eq. (12.24) is valid for all ideal gases, either m onatom ic or otherwise.
/2.4) Heat capacity of an ideal monatomic gas 505

Another relation am ong the heat capacities o f an ideal m onatom ic gas is

7 = CvICv = § = 1-667. (12.25)

This relation is followed rather closely by most m onatom ic gases, as shown in

T able 12-3 (at the end of this chapter).

E X A M P LE 12.3. The equation of state of an ideal gas in terms of pressure, volume,

and entropy.

Solution: Since entropy is a property of the state of a gas, it can be used as a variable
to define the state of a gas in the same way as pressure, volume, or temperature. From
the equation of state, pV = n RT, we have

In p + In V = In N R + In T.

Differentiation yields

f+f-f- <— »
For the case of an ideal gas, in which the internal energy depends solely on the tem­
perature, we have that dU = NCvdT. Therefore the first law of thermodynamics,
Eq. (11.37), dU = T dS — p dV, gives

NCv dT = T d S - p dV,

from which (dividing by T and using the equation of state) we obtain

nCV y = dS - nR ψ- ■ (12.27)

Eliminating dT/Τ between Eqs. (12.26) and (12.27) and using the relation Cp — Cv = R,
we have
^ + = ϋ .
p~*~ V NC v '

where 7 = CJCv- Integrating, we obtain

g
In p + 7 In V = + In (const)
Nb v
or
pVy = (const)es/NCv, (12.28)

which is the equation of state of an ideal gas in terms of p, V, and S. If a transforma­

tion is adiabatic and reversible (i.e., if it is isentropic), the equation reduces to

pVy = const. (12.29)

This equation finds many uses in processes involving gases.

506' Thermal properties of gases C12.5

12.5 llo a i Ca pa oiiion o f an Id o a l P o ly a lo m io lias*

W hen the ideal gas is not m onatom ic, we must take the structure of the molecules
into account when we calculate the heat capacities. The energy of a polyatom ic
molecule is com posed of three term s: translational energy, rotational energy, and
vibrational energy; that is,*

^niolocutc ~ E u -f- I4
Jrot T~ E vη,. (12.30)

W e shall ignore the electronic energy of the molecules because it seldom partici­
pates in the thermal excitation o f the gas. Electronic excitation requires an energy
o f the order of I cV at least; such energy is about 40 times greater than the average
thermal kinetic energy at room temperature (298°K ), and therefore a temperature
of the order o f IO4 0Iv is required to produce a substantial number of molecules in
excited electronic states (sec Exam ple 10.4). A t these temperatures, of course,
most o f the gas molecules are dissociated by collisions.
On the other hand, the rotational kinetic energy of polyatom ic molecules is of
the order IO- 4 eV, and therefore molecules can easily be carried to excited rota­
tional levels, even at temperatures that are low com pared with room temperature.
Vibrational energies are in the range of IO- 3 eV to IO-1 eV, and therefore at room
tem perature molecules m ay be found in a few low -lying excited vibrational states.
T o com pute the contribution of the internal m otions to the heat capacity of a
polyatom ic gas, we must first (using statistical methods) find the distribution of
the gas molecules among the rotational and vibrational states. Let us limit our­
selves to the simplest case of a diatom ic gas. T h e rotational kinetic energy of
diatom ic molecules, according to E q. (5.12), is

h -l(l + I)
— 21 *

where I is the moment of inertia o f the molecule relative to a perpendicular axis

passing through the center of mass and I determines the angular mom entum of
the molecule relative to the center o f mass. As explained in Section 5.7, the angu­
lar mom entum may have 21 + I different orientations, all with the same energy,
so that the y, factor used in Eq. (10.23) is 21 - f I· T h e equilibrium distribution of
the molecules am ong the available rotational states, when we use M axw eIl-Boltz-
mann statistics, is then

«ro t = (21 + l ) e - * ’ , i , + 1" 2IkT = — { 2 1 + \ ) c - u l + w ' ,T ,

^ ro t ^ ro t

(12.31)

where 0 r = h2/2Ik is called the characteristic temperature of rotation. Values of

Θ , are given in T able 12-2 for a few diatom ic gases. Looking at this table, we can

*\Vc shall assume, for simplicity, that the three energies are additive. However, strictly
speaking, there are some cross terms among the rotational and vibrational energies.
 Heal rapacities of an ideal polyatomic gas 507
i'2.5)

s'
S
S . r / Θ Γ~ 10
/
/
/
t

4 5 G 7

Fig. 12-3. Occupation of rotational levels in a diatomic gas for three values of T/S r.

see that even for hydrogen these values are very small com pared with room tem ­
perature. T h e values o f ntol are illustrated in Fig. 12-5 for three values of T /Q r.
As T increases, the number of molecules in excited rotational states also increases.
T h e rotational partition function Z rotl according to the general definition in
Eq. ( 10.22), is

Z rot = ( 2 1 + ι ) β - ' “ +'>β' / τ . (12.32)

I

Once we com pute the rotational partition function Z rott we can obtain the rota­
tional energy U lot o f the gas by using Eq. (10.24):

i rot — kX T (In .Zrot). (12.33)

508 Thermal properties of gases (/2.5

T A B L E 12-2 C h aracteristic T em p e ra tu re s fo r R o ­
tatio n a n d V ib ra tio n o f D ia to m ic
M o lecu les

Substance Sr, 0K θ ., 0K

Hydrogen 85.5 6140

Carbon monoxide 2.77 3120
Oxygen 2.09 2260
Chlorine 0.347 810
Bromine 0.117 470
Sodium 0.224 230
Potassium 0.081 140

Th e total internal energy of the gas is

U = U t r + U rot = §n R T + U tou (12.34)

since U ir = § n R T . T o obtain the heat capacity at constant volum e, Cv, we next

substitute E q. (12.34) in Eq. (12.21). T h e heat capacity increases gradually with
the temperature, as indicated in Fig. 12-6, because energy is required not only to
increase the translational energy of the molecules, but also to increase their rota­
tional energy by bringing more molecules to excited rotational levels. Figure 12-6
indicates that, at a temperature high relative to Θ Γ, C v levels off at about §/?.

Cv

F ig . 12-6. Variation of heat capacity at

constant volume of a diatomic gas due to
excitation of rotational levels.

W e can explain this as follow s: A t temperatures much higher than Θ Γ (so that
0 r/ T is very small), a very large number o f rotational states are occupied. Also
the spacing o f the rotational levels becom es very small com pared with the thermal
energy, and we m ay com pute Z rot b y replacing the summ ation in E q. (12.32) by
an integration. W e also substitute 21 for 21 + I and I2 for 1(1 + I). Then

Z rot = Γ 2l e - {e' IT)l2 dl = T / Q r.

Jo
*2.5) Heat capacities of ari ideal polyatomic gas 509

Thus In Z rot = In T — In Θ Γ and Eq. (12.33) gives

U roi = kNT = NR T t (12.35)

since IcN — NR. Then the total energy at T » Θ Γ is

U = U u + U tol = |n R T + N R T = §νΛ Τ . (12.30)

Substituting E q. (12.36) in E q. (12.21), we get

Cv = (12.37)

Thus, at temperatures high compared with 0 r, the rotational kinetic energy of a

diatom ic molecule contributes an am ount R to the heatcapacity at constant
volum e o f the ideal diatom ic gas. The same result holds true for gases com posed
of linear polyatom ic molecules.
N ow let us com pute the vibrational energy of the ideal diatom ic gas. W e as­
sume that the vibrations are simple harm onic; then the vibrational energy levels,
according to Eq. (5.16), are given by Ti1vil3 = (v + %)hu>. Therefore, when we
again use M axwell-Boltzm ann statistics and </.· = I, which corresponds to this
case, the occupation of the vibrational levels is

«vib = Ψ - = N ,-( H -i/ w e jr ( 1 2 38)

^vib ^vib

where 0 „ = ha>/lc is called the characteristic temperature for vibration. Its value
for a few diatom ic molecules is given in Table 12- 2. N ote that in all cases Θ„ is
much larger than 0 r. Also in m ost cases 0 „ is greater than room temperature.
Figure 12-7 shows the values o f Wvib for three values of T/Q v. A s T increases,
the number o f molecules in excited vibrational levels also increases; but because
0 „ > 0 r, the excited low vibrational levels begin to be appreciably populated at
temperatures at which many rotational levels are already occupied. In some
cases the molecules dissociate at energies lower than those at which the highe
vibrational levels contribute appreciably to the internal energy.
T h e vibrational partition function Z vib is

Z vib = Y j e- lv+1,2» ' IT = e ~ ° 'l2T ( 2 e ~ v%IT\ . (12.39)

V V

Using the expression for the sum of an infinite decreasing geometric progression,

Y l Xn = l + a : + x 2 -|-x3 + · · · = 7 — — > for x < I,

' I — x

and noting that in our case x = e~°°lT, we have for the vibrational partition
function
-Θ ./2 Γ
Z vib = — ------- J 7= · (12.40)
I - e *
510 Thermal properties of gases (/2.5

Γ /θ ,~ I

---------- -

Fig. 12-7. Occupation of vibrational levels in a diatomic gas for three values of T / θ„

From this result w e have

I n Z vib = -Θ ./2 T - In (I - e " 0»'7-)

and
A n n 7 I 0 V I &r/ T 2
\U1 ^ v iW 2 7 ’2 I " θ,/Γ _ j
 IIeal capacities of an ideal polyatomic gas 511

A ccording to Eq. (10.24), the vibrational energy of the gas is obtained by

1T 7 \ I I JcNQv
U vib = JcNT2 ^ (In Z vib) = ik N Q v + · (12.41)

Recalling, from Section 5.8, that ffc0 „ = %hw is the zero-point vibrational energy
of a molecule, we recognize that the term ^k N Q v is the total zero-point vibrational
energy o f the gas. This constant energy, although it may be rather large, does not
affect any process in which only energy differences are involved. T o com pute the
heat capacity at constant volum e, we must add TZvib to TZt r + TZrotl and again
apply Eq. (12.21). For large temperatures the quantity Θ υ/Τ is very small;
hence, using the approximation ez = I + x -( - · ■ · for small x, we m ay write

e* J T + (1 2 4 2 )

so that Eq. (12.41) becomes

V vib = Ρ Λ Γ Θ , + k N T = k N T ( I + Θ „ /2 Τ ). (12.43)

Thus the m olecular vibrations contribute to the internal energy by an am ount

whose value, for temperatures much larger than Θ„, is

U vib = k N T = N R T . (12.44)

T his energy happens to be the same as for the rotational energy given by
Eq. (12.35). The asym ptotic value of the total energy at very high temperatures is

U = U u + U lol + TZvib = In R T + NR T + x R T = % xR T,

corresponding to a total heat capacity

C v = IR - (12.45)

Com paring this value with Eq. (12.37), we conclude that at high temperatures the
vibrations of diatom ic molecules contribute an am ount R to the specific heat at
constant volum e of the diatom ic gas.
Figure 12-8 shows, for a diatom ic gas, Cv

the general trend of Cv as the tempera­

ture increases. This trend is well con­
firmed b y experimental measurements.

Fig. 12-8. Variation of heat capacity at

constant volume of a diatomic gas due to
excitation of rotational and vibrational
levels.
512 Thermalproperliesofgases (/2.6

IZt - I i T h o I tH n o ip Io o f E q u ip a rlition o f E n o rq q
T h e average kinetic energy o f the molecules o f an ideal gas due to their transla­
tional m otion is

E avo = %kT. (12.46)

N o w translational motion is associated with the three coordinates x, y, z required

to fix the center of mass of the m olecule. W e m ay then assume that, in view o f the
sym m etry of space, the average kinetic energy for the motion along each o f the
coordinate axes is

e = Ik T . (12.47)

Therefore, if a gas were constrained so that itsmolecules could m ove only in a

plane with tw o degrees o f freedom or coordinates, we would expect that the aver­
age kinetic energy o f the molecules would be twice e, or kT.

N ow let us consider the rotation of a diatom ic (or a linear) molecule. T h e

orientation of the axis of the molecule (Fig. 12-9) is determined by the angles a
quid β it makes with any tw o coordinate axes, such as A' and Y. Then the rotation
of a diatom ic (and in general of any linear) molecule has tw o degrees of freedom.
W e may thus expect, by extension o f Eq. (12.47) to the rotational m otion of a
molecule, that the average kinetic energy o f rotation of a molecule is

E avc(rot) = 2« = kT,

and that the total energy o f rotation o f a gas com posed o f diatom ic (or linear)
molecules would be

U rot = N E avc (rot) = k N T = n R T .

This agrees with the result given in Eq. (12.35), which is valid for temperatures
high com pared with Θ Γ.
 The principle of equiparlilion of energy 513

Similarly, the vibrational motion of a diatom ic molecule has only one degree of
freedom, and the average vibrational energy o f such a molecule should be € = \k T ;
however, in vibrational motion we have both kinetic and potential energy and their
average values are equal. Therefore the average vibrational energy of a molecule
is twice the kinetic energy per degree of freedom, or

A’ ave(vib) = 2e = kT,

and the total energy of vibration of the diatom ic gas would be

U vib = N £ avc(vib) = k N T = NR T .

This again coincides with the result given in Eq. (12.44), which is valid for tem­
peratures high compared with 0 „.
W e may then establish a very im portant rule, called the principle of equiparlilion
of energy:
A t temperatures sufficiently high so that k T is large compared with the
spacing of the energy levels associated with a certain degree of freedom
of the molecules, the average molecular energy per degree of freedom is
\kT. ( Vibrational energy contributes an amount o f energy k T per
vibrational degree of freedom because of the potential energy involved.)

This principle will help us to extend the discussion of the preceding section to
polyatom ic molecules. Consider a polyatom ic molecule which has 3 degrees of
freedom for translational m otion and / internal degrees o f freedom for rotational
and vibrational m otion (with each vibration counting as two degrees). T h e aver­
age m olecular energy at high temperatures o f a gas com posed o f such molecules
is given by

Eavc = (3 + /) e = kT,

and the total internal energy o f the gas is given by

U = W Eavc = kNT = 3 + / ^ r t

T h e heat capacity of the gas at constant volum e tends, at high temperature, to

the value

Cv = R- (12.48)

Now, according to E q. (12.24), Cp — Cy = R or Cp = C v + R, which is valid

for all ideal gases regardless o f their molecular structure. If we use Eq. (12.48)
for Cy, we obtain
514 Thermal properties of gases (12.6

Fig. 12-10. Three angles are needed to fix the orientation of a nonlinear molecule, such
as H 2O, in space.

TIie ratio 7 = Cp/Cv then has the value

y - S tr - T T f (12s0)
Actually / in these formulas corresponds only to those degrees o f freedom for
which a very large number of excited states are occupied at the given temperature.
Thus if T is larger than 0 r bu t smaller than 0 t,, / corresponds only to the rota­
tional degrees of freedom. B u t if T is much larger than 0,,, then / corresponds to
all the degrees o f freedom. F or a m onatom ic gas / = 0 and 7 = ■§ = 1.67, as
previously indicated in Eq. (12.25). For a diatom ic gas (and in general for any
linear molecule in the gaseous state), we have, at room temperature (when only
rotational m otion counts), t h a t / = 2 and 7 = £ = 1.40. If the molecule is not
linear but planar, like water (H 2O ) 1 or three-dimensional, like am m onia (N H 3),
there arc three rotational degrees o f freedom because, in addition to the angles
a and β needed to fix the axis (Fig. 12-10), we need the angle S of rotation around

TABLE 12-3 Hatios o f the Ileat Capacities for Som e Gases

Substance 7 Substance 7

Helium 1.659 Chlorine 1.355

Neon 1.64 Hydrogen sulfide 1.32
Argon 1.668 Water vapor 1.324
Hydrogen 1.410 Ammonia 1.310
Oxygen 1.401 Carbon dioxide 1.304
Nitrogen 1.404 Ethylene 1.255
Carbon monoxide 1.404
 Problems 515

the axis. Thus / = 3 and 7 = f = 1.33. Therefure the measurement of 7 can

provide im portant inform ation about the internal structure of a molecule. For
example, from Table 12-3, which gives the value o f 7 for several gases, we see that
II 2O is planar and not linear, and that the inert gases are all m onatom ic ( / = 0).
The C O 2 molecule is a notable exception because, although it is linear, it has
7 = 1.304, close to the value of a planar molecule. W e know that C O 2 is linear
because its electric dipole mom ent is zero. T h e apparent discrepancy is attribut­
able to the fact that a bending vibrational mode in C O 2 has a relatively small
vibrational energy. This vibration adds tw o degrees of freedom, and thus the
ratio o f heat capacities for C O 2 should be close to f - 1.28.5.

K e fe re a e e e

1. "The Definition of the Perfect Gas,” I’ . Landsbcrg, Am. J. Phys. 29, 695 (1961)
2. “Energy Equipartition: A Restatement," W. Lawless, Am. J. Physics, 32, 686 (1964)
3. Introduction to Chemical Physics, J. Slater, New York: McGraw-Hill, 1964, Chapters
9 and 12
4. Statistical Physics, G. Wannier. New York: John Wiley, 1966, Part I
5. The Feynman Lectures on Physics, Volume I, R. Feynman, R. Leighton, and M. Sands.
Reading, Mass.: Addison-Wesley, 1963, Chapter 41
6. Molecular Thermodynamics, J. Fay. Reading, Mass.: Addison-Wesley, 1965
7. .4 Source Book in Physics, W. Magie. Cambridge, Mass.: Harvard University Press,
1963, page 247 (Bernoulli)

K r o b le m s

12.1 Using the virial expansion for the
equation of state of a gas as given by
Eq. (12.20), calculate the work done by a
gas when it expands isothormally from a
volume F i to a volume F2. Apply the
result to one mole of hydrogen at 300°K
when it expands from a volume of 3 X IO-2
m3 to a volume of 5 X IO-2 m3. Compare
with the value obtained using the ideal-gas
expression.
12.2 An empirical equation for describing
a real gas, proposed by van der Waals, is
( p + ( F- Nf i ) = NRT.
12.3 The Boyle temperature of a real gas is
the temperature for which the second virial
coefficient is zero. Show that the Boyle
temperature is equal to a/Rb. Compute
the Boyle temperature for some of the
gases listed in Table 12-1. [Note: The
Boyle temperature is the temperature at
which a real gas may be considered as
obeying the ideal-gas equation, up to the
second order of approximation.]
12.4 The coefficient of cubical expansion
of a substance at constant pressure is
defined as

Write this equation in virial form and com­

'-7®;
pare with Eq. (12.20). Find β for (a) an ideal gas, and (b) a real
516 Thermal properties of gases
gas following the van der Waals equation
given in Problem 12.2.
12.5 The bulk modulus of a substance at
constant temperature is defined as
I I
Kr =
V \dp
Find Kt for (a) an ideal gas, and (b) a real
gas following the van der Waals equation
given in Problem 12.2.
12.6 An empirical equation of state for
real gases, proposed by Dieterici, is
p (V — N6)eNa/yjRr = NR T. Write the
equation in virial form and compare it
with Eq. (12.20).
12.7 Express the equation for an isen-
tropic process of an ideal gas in terms of:
(a) pressure and temperature, (b) volume
and temperature.
12.8 Show that the work done by an
ideal gas during an isentropic (or reversible
adiabatic) transformation is
nR (T i -
12.9 Compare the slopes of an isentropic
and an isothermal transformation of an
ideal gas at the same point in a p -V dia­
gram. Conclude from the comparison that
in an isentropic expansion of an ideal gas
the temperature decreases. Explain why
this is so.
12.10 Plot a Carnot cycle in a p -V dia­
gram when the working substance is an
ideal gas. Show that, if T i, V 2, Vs, and
V 4 are the volumes of the gas at the end
of each transformation, then
V 2Z V 1 = F 3 / F 4 .
12.11 Compute the work done by the gas
during each of the transformations com­
posing a Carnot cycle, and show that the
net work done is
I
W = N R ( T 2- T i ) In V 2/V Assume
\/erify then that Eq. (11.47) is satisfied.
[Hint: Use the result of Problem 12.10.]
12.12 The adiabatic compressibility of a
substance is defined as
K, =
V\dp
Find Ks for an ideal gas. The propagation
of elastic waves in a gas is an adiabatic
process and the velocity of propagation is
given by v = V KsZp, where p is the density.
Explain how, by measuring v, one can
compute 7. Show that v depends only on
the absolute temperature.
12.13 An ideal gas at 300°K occupies a
volume of 0.5 m3 at a pressure of 2 atm.
The gas expands adiabatically until its
volume is 1.2 m3. Next the gas is com­
pressed isobarically up to its original
volume. Finally the pressure is increased
isochorically until the gas returns to its
initial state, (a) Plot the process in a p-V
diagram, (b) Determine the temperature
at the end of each transformation, (c)
T 2)7 - I). Find the work done during the cycle. As­
sume that 7 = 1.4.
12.14 An ideal gas at 300°K occupies a
volume of 0.5 m3 at a pressure of 2 atm.
The gas expands adiabatically until its
volume is 1.2 m3. Next the gas is com­
pressed isothermally until the volume is
the same as the original volume. Finally
the pressure is increased isochorically
until the gas returns to its initial state.
(a) Plot the process in a p -V diagram.
(b) Determine the temperature at the end
of the adiabatic expansion, (c) Find the
work done during the cycle. Assume that
7 = 1.4.
12.15 An ideal gas is initially at T 1 =
300°K, P 1= 3 atm, and V 1 = 4 m3. The
gas expands isothermally to a volume of
16 m3. This is followed by an isochoric
process to such a pressure that an adiabatic
compression returns the gas to the original
state. i. that all the processes are
 Problems 517

reversible, and do the following: (a) Draw 12.21 Show that the vibrational heat
the cycle on a and a of a gas at constant volume is
p-V diagramcapacity
diagram, numerically labeling all end­ given by
points carefully, (b) Calculate the work Ιίω/JcT

done and the entropy change during each C V , vib = R flu /k T

process and during the cycle. Assume that (e I)
T = 1.4.
Find the limiting values for Γ « 0„ and
12.16 Estimate the error made in evalu­
τ y,> Θν.
ating Zrot when 21+ I is replaced by 21
and 1(1 + I) is replaced by I2 in Eq. (12.32). 12.22 Using the result of Problem 11.13,
show that the entropy of a diatomic gas
12.17 Calculate the percentage of mol­
due to molecular rotations is
ecules of a diatomic gas in the ground
(I = 0) and first excited ( 1 = 1) rotational Srot = k N[ l + In (T/Or)].
states at temperatures T = S r and T = 2©r.
12.18 Compare the number of hydrogen [Note: When the molecule is homonuelear,
molecules per mole in the second excited it can be shown that we must use T /20r;
rotational state (I = 2) with the number of this is due to a halving of the distinguish­
chlorine molecules per mole for the same able states as a result of the symmetry of
excited state when the temperature is the molecule.]
300°K. 12.23 Using the result of Problem 11.13,
12.19 Compare the number of hydrogen show that the entropy of a diatomic gas
molecules per mole in the second excited due to molecular vibrations is
vibrational state (v = 2) with the number
Svib = k N [(® v/T)(eQ»/T - I)
of chlorine molecules per mole for the same
- In (I -
excited state when the temperature is
300°K.
Verify that for small temperatures Svib
12.20 Consider a mole of CO gas. Calcu­ tends to zero, while for large temperatures
late the number of molecules in the first Svib approaches the value
three vibrational energy states at room
temperature (300°K) and at IOOO0K. k N [I + In ( Τ / Θν)].
516 Thermal properlie- 13
* St'
given ID4
Λ
UM STATISTICS
•S'Sk 0v^
1° ' /
Λ >

13.1 Introduclion
13.2 Fermi-Dirac Distribution Law
13.3
13M Application of Fermi-Dirac Statistics to Electrons in Metals
13.5 Bose-Einstein Distribution Law
13.6 The Photon Gas
13.7 Heat Capacity of Solid
13.8 The Ideal Gas in Quantum Statistics
13.9 Comparison of the Three Statistics
 Fermi-Dirac distribution law 519

13.1 In trod u ction

In Chapter 10 we discussed classical statistics, which is characterized by the

m ethod of calculation of the probability of a given partition, stated in Eq. (10.8),
and by the M axwell-Boltzm ann distribution law, Eq. (10.9), for the most probable
or equilibrium partition. W hen we discussed classical statistics, we ignored any
sym m etry considerations related to the distribution of the particles am ong the
different states associated with each energy level accessible to the particles. H ow ­
ever, as we said in Chapter 4, there may be certain restrictions on the number of
different ways in which a group of particles may be distributed am ong the avail­
able wave functions associated w ith each energy state. Clearly these restrictions,
of quantal origin, affect the probability of a given partition. T h e theory in which
these sym m etry considerations are taken into account is called quantum statistics.
There are tw o kinds of quantum statistics: One concerns particles obeying the
exclusion principle, and hence described b y antisymmetric wave functions! This
kind is called Ferm i-D irac statistics,) and the particles are called f e r m i o n s T he
second concerns particles not restricted by the exclusion principle, and described
by symmetric wave functions. This kind is called Bosc-Einstein statistics, and the
particles are called bosons. In both kinds of quantum statistics it is assumed that
the particles are identical and indistinguishable. A t high temperatures and low
densities, classical statistics and the tw o kinds of quantum statistics give prac­
tically the same results.
In this chapter we shall briefly discuss both kinds of quantum statistics and
apply them to a few im portant physical problems.

13.2 F c r m i-U ir a c D istribu tion L a ir

Let us re-evaluate the probability of a partition of a system of particles, assuming

that the particles are identical and indistinguishable. In addition, we assume that
the particles obey the exclusion principle, so that no two particles can be in the same
dynam ical state and the wave function of the whole system must be antisymmetric.
Particles satisfying all these requirements are called fermions, after the Italian-
born Am erican physicist Enrico Fermi (1901-1954), who first discussed these
systems. It has been found experimentally that all fundamental particles with
spill J are fermions.
T o com pute the different and distinguishable ways in which a system of fer­
mions m ay be arranged for a given partition, we must revise our definition of the
intrinsic or state probability </,·. In quantum statistics, </, is given by the different
quantum states corresponding to a given energy; i.e., the degeneracy o f the energy
state. T o each quantum state there corresponds a particle wave function. These
wave functions in turn are determined by each of the possible arrangements of
quantum numbers corresponding to a given energy level. For example, for parti­
cles of spin i , not subject to magnetic forces, each particle may be in each energy
state with spin up or dow n (m , = ± 4 ) , and so </,· = 2. For m otion in a central
field, the energy is independent o f the orientation of the orbital angular m om entum ,
.'>20 Quanlum statistics ( 13.2

which introduces a degeneracy equal to ‘2 1+ I, which is the value of y for that

energy state. W c used this result in Section 12.5 when we discussed the rotational
partition function of molecules. If the particles have spin, the total degeneracy is
2(21 + 1 ) . If, in addition, several angular mom entum states are com patible with
the same energy, as in a coulom b field, larger values o f y, result. Since the exclu­
sion principle forbids that tw o particles be in the same energy state with the same
quantum numbers, the g,·’* give the maximum number of particles (fermions) that ran
be accommodated in an energy level without violating the exclusion principle. Therefore
the X1 values o f a given partition cannot exceed the </,· corresponding to each energy
level; that is, x, < ;/,.
T o fill the energy level Ii, with n, particles, we note that we can place the first
particle in any o f the y, states available; i.e., we can assign it any o f the ff,- sets of
quantum numbers available. T h us we can place the particle in one of y, different
ways. The second particle can go into any o f the </,· — I remaining states. T h e
third particle goes into any of the y, — 2 remaining states, and so on, until all n,·
particles arc placed in the energy level. T h e total number of different ways of
arranging the x, particles am ong the g, states with energy E, is thus

QiiSi — l ) ( 0i — 2 ) · · · (ffi — w,· + I),

which can be written in the form

ffi-
(13.1)
(fir.· — n,

So far we have taken the exclusion principle into account. If, in addition, the
particles are indistinguishable, it is not possible to recognize any difference if the
M1- particles are reshuffled am ong the states they are occupying in the level of
energy /i, (this number is »,!, as we saw when we discussed the .Maxwcll-Boltzmann
distribution law). Therefore we can obtain the total number of different and dis­
tinguishable arrangements o f x, identical particles am ong the ff, states o f energy
E i by dividing expression (13.1) by »,·!, resulting in

(13.2)
Wi Kfir,- — « ; ) !

W e can find the total number o f distinguishable different ways of obtaining the
partition n t , n2, n3, . . . am ong energy levels E it E 2, E 3, . . . by m ultiplying all
the expressions like E q. (13.2) for each o f the energy levels available, thus giving
the partition probability as

P _ _____ ffi! ____ff21______________ ffsl

W iK ffi — W i)! W2 K ff2 — W2 ) ! W 3K f f 3 - W3 ) !

r sA _____ (13.3)
= I II W fK ff1- — W ,)!

Then, as we did with the M axwell-Boltzm ann distribution law in Chapter 10, we
must find the most probable partition by com puting the maximum of In I 1. (W e
 Fermi-Dirac distribution law 521

shall do this in Exam ple 13.1.) The result is that the most probable partition cor­
responds to the numbers

this constitutes the Fenni-D irac distribution law.

T h e parameter β here plays the same role it has in the M axwell-Boltzm ann
distribution law, Eq. (10.9). Therefore we again define the temperature o f the
system of fermions in statistical equilibrium by Eq. (10.23); that is,

k r = ι/β.

T h e quantity a is still determined by the requirement that )Γ, n ,■ = N . In most

cases a is a negative quantity. H ow ever, one usually defines a quantity eF, having
the dimension of energy, which is related to a by the equation

6F = —OtkT.

Then Eq. (13.4) becomes

The energy eF has a positive value in m ost cases, and plays a very im portant role
in physical applications; it m ay be considered as practically independent o f tem­
perature. W e observe from E q. (13.5) that, for T — 0 all energy states up to
E = «I.· are fully occupied («,· = </,·), while all the states with E > ίρ are em pty
(n, = 0). The reason for this is that

for E i — i F < 0 ,
for E i — ep > 0 .

This situation is shown in Fig. 13-1, in which the distribution function /!,/</, is
plotted for different temperatures. As a contrast, recall that in M axw ell-E oltz-
mann statistics, at T = 0, all particles should be at the ground energy level. In
Ferm i-Dirac statistics this accum ulation at the ground level is prevented by the
exclusion principle, and the particles at T = 0 occu py the lowest energy levels

"I/Bi
T=O

Fig. 13-1. Distribution function m/gt

at three temperatures in Fermi-Dirac
statistics.
522 Quanlum statistics (13.3

available up to the energy ep. Hence the energy Cf gives an indication of the
m aximum energy of the fermions in the system. Therefore is equivalent to the
Fermi energy, which we introduced in Section G.4 when we discussed free elec­
trons in metals, and hence we shall give it the same name here. A t higher tem­
peratures, states with energies greater than « f begin to be occupied, by a transfer
of particles from states o f lower energy. However, essentially oidy those states
with energy close to Cp are affected for temperatures such that k T « e*·. T h e
reason for this is that all low-energy states are fully occupied and the exclusion
principle prevents the addition o f further fermions to those states. Thus, as shown
by the curves in Fig. 13-1, only those fermions with energy close to C f can m ove
into higher unoccupied states by absorbing the relatively small energy kT. The
temperature 0 f , for which k Q y = Cf, is called the Ferm i temperature.

E X A M P L E 13.1. Derivation of the Fcrmi-Dirac distribution law.

S olu tion : The problem, as in the case of Maxwcll-Boltzmann statistics (Example 10.1),
consists in finding the maximum of In P subject to the conditions that Σ ί η > = A and
Σ · niE , = U. First we obtain In P 1 using Stirling’s approximation In ad = x In x — x.
AVe thus find that

In P = ? . Igi In s,· — n; In n,- — (g,· — n.) In (0, — n,)].

Next we compute —d(ln P ) and equate it to zero, to obtain the maximum of P,

—d(ln P ) = [In n; — In (0; — n,·)] dn, = 0. (13.6)

i

When we combine Eq. (13.6) with Eqs. (10.15) and (10.17) (that is, Σ ί dn· = 0 and
Σ ί Ei dn, = 0), which again hold in this case, multiplied, respectively, by the factors a
and /3 (recall Example 10.1), we then arrive at

In n,- — In (g, — n,) + a -f- βE i = 0

or
it,· —a —SE:
----------- = e
?. — » f

Solving for n „ we finally obtain Eq. (13.4).

T/m> K l v r l r o n Has
T h e most characteristic system of fermions is that of electrons in a metal, since,
as we saw in Chapter 4, electrons obey the exclusion principle. In Chapter 6 we
considered the energy levels of the electrons in a metal and showed that they
are grouped in bands. T h e lower bands are filled with electrons at practically all
temperatures and we do not have to consider them. B ut the upper band is only
partially filled with electrons up to a certain energy level. On that basis we intro­
duced the concept of Fermi energy in Section 6.4.
 The electron r/as 523

W e must consider only the dist ribution o f electrons am ong the continuous range
of energy levels in the upper or unfilled band, also called the conduction band.
W c shall therefore place our zero of energy at the bottom o f the conduction band.
W c shall also assume that the electrons m ove freely within the conductor, so long
as their energy falls in this upper conduction band. This is a reasonable assump­
tion, which was fully justified in Chapter 0. Again, since the energy spectrum of
the electrons in the band is practically continuous, we must replace <j, b y 17(E ) dE
in Ecp (13.5), as we did previously for an ideal gas. Thus the number dn of elec­
trons with energy between E and E + dE is

O(E) dE
dn - (13.7)
;( E —i p ) l k T I

where the energy E is measured from the bottom of the conduction band and
f/(E) dE gives the number of stales in the energy range between E and E + dE.
F or (/(Zi) dE we may again use expression (10.39), but we must multiply it- by 2
to take into account the two possible orientations of the spin of the electrons,
each giving rise to a different state for the same energy; that is,

g ( E ) d E = 8ir V { \ f )V1i E 1' 2 dE. (13.8)

Λ*

If we substitute Eq (13.8) in E q. (13.7), we obtain the num ber dn/dE of free

electrons per unit energy range as

1/2
dn 8 ttF(2 w 3) 1' 2 E
9( E —tp )lk T
(13.9)
dE h 3
+ 1

T his Ls the Ferm i-D irac formula for the energy distribution of free electrons, or,
in general, o f free fermions. It is represented in Fig. 13-2 for T = 0, for a low
temperature, and for a temperature high com pared with Θ ρ = fr/ k . W e have
already considered this distribution in Section 0.7 in a qualitative way, when we
were discussing electrical conductivity.
T h e Fermi energy as a function of the temperature may be obtained b y requir­
ing that Eq. (13.9), integrated over all energies, give the total num ber N of elec-
dn
dE

Fig. 13-2. Energy distribution of a

system of fermions at three tempera­
tures.
524 Quantum statistics (13.3

Τ Λ Β Ι.Ε 13-1 Ferm i E nergy an d F erm i T e m p e ra ­

ture o f Several M etals

Metal CF, eV 0 F, 0K

Li 4.72 5.5 X IO4

Na 3.12 3.7
K 2.14 2.4
Cu 7.04 8.2
Ag 5.51 6.4
Au 5.54 6.4

trons in the conduction band. Assuming that Cf is practically independent of T,

we may com pute N at T = 0. (W e did this in Section (5.4.) The result is

'lV 3-v Y ' 3 m im

t F = 8 ^ U V · ( 1 3 1 0 )

Thus we can obtain the Fermi energy of electrons in a metal if we know the num­
ber N /V of conduction electrons per unit volum e. T able 13-1 gives values of Cf,
as well as of the Fermi temperature, Θ ρ, for several metals.

E X A M P L E 13.2. Determine the total energy of a group of N fermions at very low

temperature.
S olu tion : The total energy U is given by

U
- / “ " - i E f E iE ·
Since the temperature is very low, we may use (as a good approximation) the value of
dn/dE for T = O, which is just g(E). Thus

dn 8irF(2m3) 1/2 1/2

dE P b ■

Also we integrate only from 0 to cf- Thus

f/ = W p l f F E 312 dE = **■
Ii3 Jo oh3

We may write this expression, using Eq. (13.10), as

U = f.V«F,

which is the minimum energy of a system of N fermions. The average energy per particle
13.3) The electron gas 525

E X A M P L E 13.3. Doteimino the kinetic energy of the nucleons in a nucleus, assuming

that there are two systems of fermions (neutrons and protons) at very low temperature.

S olu tion : We may use Eq. (13.10) to eliminate in the expression for U obtained in
the previous example by writing

u = — ( - Y ' 3— —
40 \tt/ m V2/3

In the nuclear case we have two kinds of particles, neutrons and protons, their numbers
being Ar and Z, and the volume V is common for both. Thus, neglecting the slight mass
difference of the two particles, the total kinetic energy is

3 /.3 \ 2/3 A2 A' 5/3 + Z 5/3

~ 40 V 7 m V'2/3

But [recall Eq. (7.2)] the nuclear volume is V — girR 3 = . Therefore

3 / 9 \ 2/3 Ii2 Af5/3 + Z 5' 3 .V5/3- f Z 513

'"40 U 2/ mrl A 2/3 A 2' 3 ’
where

‘·ϊ(έΓ5·“ χ'Γ"’",'Μ
We know that /I = .V + Z. On the other hand, let us call D = N - Z . Thus

N = £ (A + D) and Z = £(.4 - D),

so that

N = £A ( l + j \ and Z = £.4 ( l - j ) ■

Substituting these values in the expression for U1 we obtain

Using the binominal expansion (I + x )n = I + nx + £n(n — l) x 2 + · · · , and keeping

in mind the fact that D/A is, in general, small compared with unity, we obtain

(. , D V /3 , I5 D 5 D 2
V1 + lJ = 1 + 3 A+ 9 A * + ' " ’

(\_£\5'3 _ί H■§ _
v a ) _ 3 A 9 A2

Thus, to the order of approximation we have chosen,

~\2 I .. cm
U1 = 2 ~ 2/3c A ( , + . . ] = 2 - 2/3c A + ( 2 _2/3 c) I + ·
526 Quantum statistics

The first term gives an energy proportional to the total number of particles, while the
second gives a contribution proportional to the difference N — Z. Recalling our dis­
cussion of Section 7.5, we recognize that the first term is included in the term propor­
tional to A in the total energy formula, Eq. (7.11), while the second term corresponds to
a\(N — Z ) 2/A, so that

04 = f ( 2 - 2,3c) = 8.33 MeV.

This value is about one-third of the empirical result for 04. This disagreement is not
surprising when we consider the crudeness of the model used.

I.'t. I A p p U ra tio n o f F r r m i -IU r a r StatiMiirs

to E lrriro n s in Alrtals
W e shall now consider some physical effects in metals, effects that are explainable
in terms o f Ferm i-D irac statistics applied to the free electrons in metals. Fig­
ure 13-3 shows a plot of the potential energy of an electron both inside a metal
and at the surface. T h e potential energy near the surface is given by the curve
A B . A t normal temperatures the conduction band is essentially filled with elec­
trons only up to the Fermi energy Cf, as shown by the distribution curve in part (b).
T o extract an electron from the metal it is therefore necessary to give the electron
at least the energy designated in Fig. 13-3 by e<fi. T h is is, for example, what hap­
pens in the photoelectric effect (discussed in Section 1.4), in which photoclectrons
are emitted only if hv > e<t>. The quantity φ is called the work Junction o f the
metal. A t high temperatures, however, the occupation o f electronic states extends
over energies well above ίρ· If the temperature is high enough, some electrons ac­
quire energies larger than ep + εΦ and escape from the metal. This is the process
called thermionic emission, and it is fundamental to the operation of electron tubes.
Using the Fermi-Dirac distribution law to com pute the num ber of electrons
arriving at the surface of the metal with enough energy and a direction of motion

H E

Fig. 13-3. Conduction baud in a metal at room temperature.

i3 A ) Application of Fermi-Dirac statistics to electrons 527

T A B L E 13-2 V alu es o f the W o rk F u n ction φ a n <j the

T h e rm io n ic C o n stan t A, O b tain e d Ex­
perim e n tally fro m Eq. (13.11)

Metal φ, cV A, A cm -2 0K -2

Cs 1.8 120
Cr 4.4 48
W 4.5 75
Pt 6.2 32
Ta 4.1 55
Ni 4.6 30
Ca 3.2 60
Th 3.4 60
Mo 4.3 60

to escape, we can obtain the thermoelectric current density j com ing from the
metal surface in terms of the temperature o f the metal. The result is

j = { k T ) 2e - '* l k T = A T 2e - « , k T t (13 n )

which is called the Richardson-Dushman equation. This equation is not obeyed

rigorously, for several reasons. In the first place, electronic emission is very sensi­
tive to surface conditions as well as to the orientation of the surface relative to the
crystal lattice of the metal. Also, as the temperature increases, the work function
varies because of the increase in the number of electrons having an energy above
the Fermi level. T able 13-2 gives some experimental values of φ and A for sev­
eral metals. T h e use of M axw ell-Boltzm ann statistics gives a different tempera­
ture dependence, and thus thermionic emission is an indirect proof of the fact that
electrons follow Ferm i-Dirac statistics.
Another illustration of the existence of a Fermi energy in metals is the contact
potential difference between tw o metals. Suppose that we have tw o metals A and
B, not connected electrically (Fig. 13-4a). In the absence of any external electric
field, the potential energy o f an electron outside the metals is zero and the respec-

Fig. 13—1. Origin of the contact potential difference.

528 Quantum statistics (/ 3.5

tive Fermi levels of the metals are at energies εφΛ and e<t>a below the potential
energy outside the metals. Let us suppose that Φη is larger than Φ..|. Then when
the metals arc n ot connected the Fermi level of A lies higher than the Fermi level
o f B. When the tw o metals are connected electrically (Fig. 13—lb ), the more
energetic electrons from A will flow or diffuse into Ii, filling the levels above the
original Fermi level o f B and em ptying the upper levels in the conduction band
of A . Equilibrium is reached when the upper occupied levels o f the conduction
bands in A and B are equalized. H ence metal A , which has the smaller work
function, becomes positively charged, and metal I i 7 which has the larger work
function, becomes negatively charged. This results in a potential difference be­
tween the tw o metals, which is essentially equal to Φη — Φλ, in agreement with
the experimental value. T h e potential energy o f an electron as it m oves from one
metal to the other, across the space between them, after equilibrium is attained,
is shown by the solid line in Fig. 13—1(b).

I It.S U o s v -E in M lo in U i s lr i b u l io n L a i r

Experience has shown that there are systems com posed o f identical and indistin­
guishable particles that are not restricted by the exclusion principle. In such
systems there is no limit to the number of these particles that can be in the same
quantum state. The wave function describing such a system of particles must be
symm etric. Particles satisfying these requirements are called bosons, after the
Indian physicist S. N. Bose (1894- ), who first investigated the statistics of
this kind o f particle. It is found experimentally that all particles with integral
spin (0 or I) are bosons. Thus helium nuclei and mesons are examples of bosons;
4He and H 2 gases also obey Bose-Einstein statistics.*
In Bose-Einstein statistics, as in Ferm i-D irac statistics, the g.’s give the degen­
eracy of each energy level. T o com pute the different and distinguishable ways in
which a system of bosons may be arranged to produce a given partition, we first
evaluate the number of distinguishable arrangements of n,- particles am ong the
( ji states corresponding to the energy level I i1 - which result in symm etric wave
functions. This number of arrangements is equal to the number o f ways n, identical
objects may be distributed am ong </,· boxes, without limit to the number o f objects
in a particular box. T o obtain this number we proceed as follows: Suppose that
we place the n, particles in a row and distribute them in the </,- quantum states
available b y placing </,· — I divisions at appropriate places, as shown below for

* That a nucleus such as 4He, composed of four fermions, must be a boson can be seen
very easily. Consider the wave function describing two helium nuclei. To interchange
the two nuclei, we must interchange all the fermions. Every time we exchange two fer­
mions the wave function of the system changes sign. But since there are four pairs of
fermions in the system, the exchange of all fermions leaves the wave function unchanged.
That is, the wave function of the system is symmetric in the two nuclei, although it
is antisymmetric in each pair of fermions. This logic applies to any system in which
“ particles” (nuclei, molecules, etc.) are composed of an even number of fermions. Such
“ particles” then behave as bosons.
13.5) Bose-Einslein distribution law 529

a particular case:

T he total number of possible arrangements of particles and divisions is equal to

the number o f permutations of n,- + Jr1 - I objects in a row, which is (n, + </,·— I)!.
B ut because the particles are identical and indistinguishable, all permutations that
differ only in the ordering o f the particles are the same. Hence we have to divide
the above number by nil. In addition, all permutations of the divisions yield the
same physical state. So we must also divide by (</,· — I)!. T h e total num ber-of
distinguishable arrangements o f the n,· particles am ong the </,· states therefore has
the value I C~ \~\
IΟ. Λ
+ Qi — II)!
U - Θ ..' · *

w,■!(?.· — I )!
(\ ( I (13.12)

W e obtain the total number of distinguishable different ways o f form ing the par­
tition Ti1, Ti 2 , Ti3 , . . . am ong the energy levels E il E 2, E 3, . . . as we did before, by
multiplying all the expressions like Eq. (13.12) for each of the energy levels avail­
able, resulting in a partition probability of

p _ (n i 9i — I) I (n 2 + 92 — I)! (^3 + 93 — 1)1

niKgi — I)! n 2l(g2 — I)! n 3 \(g3 — I)!

_ T f (” < + !?.· - D ! . T13 I o')

U i Kgi - I)!
«

Our next step is to find the most probable partition by com puting the maximum
of In P . (W e shall do this in Exam ple 13.4.) T h e result is that the most probable
partition corresponds to the numbers

” ·· = (1 3 1 4 )

this constitutes the Bose-Einstein distribution law.

The parameter β plays the same role here as it did in the M axwell-Boltzm ann
and Ferm i-D irac distribution laws, and w e again define the temperature o f the
system of bosons in thermal equilibrium by E q. (10.23); that is,

kT = 1/β.

Then E q. (13.14) becomes

n‘ = +EifkT J (13.15)

T he constant a, as before, is determined by requiring that n, = N ; a does not

have a special meaning in Bose-Einstein statistics as it does in Fermi-Dirac statis­
tics. Because Ti, cannot be a negative number, a must be positive.
530 Quantum statistics ( 13.5

m/gi

T h e distribution of bosons follows the trend indicated in Fig. 13-5, in which

the distribution function n,■/(/,· is plotted for tw o temperatures. T h e Bose-Einstein
distribution tends to emphasize the lower energy levels more than the M axwell-
Boltzmann distribution does, because of the negative sign in the denominator.

E X A M P L E 13.4. Derivation of the Bose-Einstein distribution law.

S olu tion : This problem, as in the previous two cases (Examples 10.1 and 13.1), con­
sists in finding the maximum of In P subject to the conditions that Σ ι «· = N and
Σ · n-iEi = U. First, using Stirling’s formula, we compute In P , and obtain

In P = [(«■' + Si — I ) ln (n· + Si — Ο
I
— n, In m — (gi — I) In (9, — I)].

Next we obtain the maximum of P by setting (/(In P ) equal to zero. The result is

—d(ln P ) = ^ (—In (n,· + gi — I) + In n,·] dm = 0. (13.16)

I

The next step is to combine Eq. (13.16) with Eqs. (10.15) and (10.17) (that is, Σ < dtii = 0
and Σ · E i dn, = 0), which express the conservation of the number of particles and of
energy, multiplied by a and β, respectively. This results in

— In (n, + 9, — I ) -f- In n,- + a+ /3/i, = 0 .

If we assume that n, - f 9,· is very large compared with I, we may neglect the I in the first
term in the above equation and we have

• Wf λπ —a —βΕ:
In :— = —a — βΕί or ----- ;— «= e
n. + 9. «1 + Si

Solving for n,·, we obtain Eq. (13.14).

13.6) The pholcn gas 531

13.0 Th*· V h o t o n G a *

Perhaps the m ost im portant application of Bose-Einstein statistics is to the analy­

sis of electrom agnetic radiation trapped in a cavity and in thermal equilibrium
with the atom s of the walls of the cavity. As we said in Section 1.3, this is called
blackbody radiation. The atom s of the walls of the cavity arc continuously absorb­
ing and re-emitting radiation until equilibrium is reached; this happens when the
rates o f emission and absorption of radiation are the same. At equilibrium the
spectrum o f the trapped electromagnetic radiation has a well-defined energy dis­
tribution ; that is, to each frequency there corresponds an intensity o f blackbody
radiation which depends solely on the temperature of the walls and is independent
of their material.
In Section I.!) we saw that when electrom agnetic radiation interacts with mat­
ter, it behaves as if it were com posed o f "particles” called photons, each o f m om en­
tum h/\ and energy hv, where λ is the wavelength and v the frequency of the
radiation. W e may then assume that the equilibrium blackbody radiation behaves
as a photon gas. T h e photons are assumed not to interact among themselves,
only with the atoms of the wall. Since photons are not distinguishable and nothing
prevents many photons having the same energy (experience tells us that the in­
tensity of the radiation at each frequency m ay be increased without lim itation),
photons can be considered as bosons, obeying Bose-Einstein statistics.
One characteristic situation must however be taken into account in this case.
Tlie number of photons is not constant, since they can be cither absorbed or emitted
by the atom s in the walls of the cavity. Therefore condition (10.15), Σ , dn, = 0,
must be dropped; this means that the parameter a is not necessary. Then we
must set a = 0 in E q. (13.15), so that n, = </,/(e K' lkT — I). In addition, the
energy spectrum of the photons m ay be treated as continuous if the cavity is
large com pared with the average wavelength of the radiation, since in this case
the energy difference between successive allowed energy values or wavelengths is
extrem ely small (recall Fig. 2-1 0).
Under these conditions we must write E q. (13.15) with g, replaced by g (E ) dE,
resulting in

d n - (13.17)
e - I

Because the energy o f the photons is related to the frequency by E = hv, we may
introduce a function g(v) such that g (E ) dE = g(y) dv, where g(v) dv gives the
number o f oscillatory modes in the frequency range dv corresponding to the energy
range dE. W e previously obtained the num ber o f oscillatory modes for waves
trapped in a cavity o f volum e V in E q. (2.20), but we must multiply by 2 to
account for the tw o independent directions o f polarization, since electromagnetic
waves are transverse. Therefore the number of states in the blackbody radiation
with frequency between v and v + dv or energy between E and E + dE is

g (E ) dE = g(v) dv = v2 dv. (13.18)

Cj
532 Quantum statistics (13.6

Therefore we may write Eq. (13.17) as

Th e energy corresponding to dn photons in the frequency range dv is (hv) dn and

the energy per unit volum e is (hv) dn/V. Finally, the energy density distribution
e ( v ) in blackbody radiation is defined by

. . hv dn
V T v'

so that e ( v ) dv gives the energy per unit volum e corresponding to radiation with
frequency between v and v + dv. B y virtue of Eq. (13.19), this energy density is
given by
I
(13.20)
eh" kT - I

This is the celebrated Planck radiation equation, which was stated without proof
in Eq. (1.8) and is represented in Fig. 1-5 for different temperatures. T h e agree­
m ent of Eq. (13.20) with the experimental facts is strong support for the idea of
radiation as being com posed o f photons that obey Bose-Einstein statistics. W e
remind the student that it was the problem of blackbody radiation which prom pted
Planck to assume that when radiation interacts with m atter it is absorbed or
em itted in energy quanta equal to hv. H ow ever, Planck’s original derivation is
not considered sound because, on one hand, he assumed that the atoms o f the
walls of the cavity acted as oscillators with an energy E — nhv instead of an energy
E = (n + $)hv, an^ because, on the other hand, he used M axwell-Boltzmann
statistics. Surprisingly, his result was correct. B ut if the zero-point energy \hv
is included in Planck’s calculations, the resulting expression is no longer satisfactory.
Th e problem had to wait several years until a satisfactory proof, as given in the
text, was found.

E X A M P L E 13.5. Discussion of spontaneous and induced radiative transitions.

Solu tion : In Section 1.7 we explained that a system in an excited energy level may fall
to a lower energy level spontaneously, or it may be induced (or stimulated) to jump into
the lower level with the emission of radiation, if radiation of the proper frequency is
present.
2 atom s
-V

.-Igl + # 2 1 Kt 1') H i 2 E(v)

Fig. 13-6. Induced and spontaneous transitions. -V, atom s

 The photon gas 533

L e t us consider tw o levels o f energies Ei and E 2, occupied by Ni and Ν·2 atoms, re­

spectively (F ig . 13- 6). T h e photons corresponding to transitions between these tw o
levels must have an energy he = E 2 — E i. A to m s at level Eo may jum p spontaneously
into level E\. L e t us call /I21 the corresponding spontaneous emission transition prob­
ab ility per unit tim e. I f radiation o f frequency e is present and its energy density is e (v ),
absorption transitions from E i in to E 2 are produced. I t is natural to assume th at the
number o f such transitions per unit tim e is proportional to the energy density e (j> ) ; that
is, the induced absorption transition probability per unit tim e is B 1 2 E M , where B 12 is
the transition probability per unit tim e and unit in ten sity o f the radiation. B u t the
radiation, because o f its interaction with excited atom s at level E2, also produces emission
transitions from E2 to Ei w ith an induced emission transition probability per unit tim e
Β 2 1Φ ). T h erefore the total emission p ro b a b ility per unit time, from level E 2 to level
E 1 is A 21 + B 21e(v). I f there are N 2 atoms in level E 2, the number o f atom s that jum p
per unit tim e from E2 to E i is [A 21 + B 2I K M jA r2- A t the same tim e, the number o f
atoms that jum p from E i to E2 per unit tim e is B 12κ M A' 1. Therefore the net change
per unit tim e o f atom s in level E 2 is equal to the rate o f gain by absorption minus the
rate o f loss b y emission, or

= B 12E M A rl — [ .4 21 + Β 2ιε Μ ]Α Γ 2,
Absorption Emission

with an equal (b u t opposite) gain for the low er level. W hen equilibrium is established
between the atom s and the radiation, we must h ave dN2/dt - 0, or

B l2EMAT1 = [A 2 1 + B 2ik M );V 2,

so th at the number o f absorption and emission transitions per unit tim e between the tw o
levels is the same. I f the atom s are in therm al equilibriu m and follow .M axwell-Boltzm ann
statistics (which is a reasonable assumption in m ost cases), then

N i/N2 = = eMkT,

so that

B iiE (y )e ’lkT = Au + Β21Φ) ( 13.21)

, . A21/B12
K(e)
e ’,tT - B21/B12

W hen w e com pare this with E q. ( 13.20), which gives the energy density for radiation in
equilibrium with m atter, we find that

/!21 Srrvi B 21
B T 2 = a n J B T 2 =

a result first obtained b y Einstein in 1917. T h e second relation shows that the induced
emission and absorption probabilities per unit tim e are equal. T h e calculation does not
allow us to obtain the values of A 2 1, B 2i , and B i 2. T h e y must be derived using quantum-
mechanical considerations.
534 Quantum statistics (13.6

From Eq. (13.21),'with B i2 = B 21, we obtain the ratio between the spontaneous
emission probability A 2i and the induced emission probability B2ie ( v) when matter is
in equilibrium with radiation as

Spontaneous emission probability _ A 21 _

(13.22)
Induced emission probability B2ie ( v)

Therefore if Iiv 3i> kT, spontaneous emission is much more probable than induced emis­
sion, which can then be completely neglected. This holds true in the case of electronic
transitions in atoms and molecules and in the case of radiative transitions in nuclei. But
if hv« kT, as it is in the microwave region of the spectrum, induced or stimulated
emission may become important.
Induced emission is the result of the action of the incoming radiation on the atoms (or
molecules) of the substance. Hence the forced atomic oscillations bear a constant phase
difference relative to the incoming radiation. This means that all atoms radiate in phase,
and therefore induced emission is coherent. On the other hand, spontaneous transitions
occur at random, with no correlation between the times at which atoms undergo transi­
tions. Therefore the phases of atomic radiations are distributed randomly. We then say
that spontaneous emission is incoherent.

E X A M P LE 13.6. Discussion of masers and lasers.

Solu tion : As explained in the preceding example, when radiation and matter are in
thermal equilibrium, no net absorption or emission occurs because the total number of
absorption and emission transitions per unit time is the same. This is indicated in
Fig. 13-7(a). Although the induced transition probability may be smaller than the
spontaneous transition probability, absorption matches emission because of the large
population of the lower level at thermal equilibrium. In the general case, in which radia­
tion interacts with matter without necessarily being in equilibrium, we have

Emission rate _ (.421 + /ieiF.fidlA^

Absorption rate B t2E (v)N t l)
■421 \ X 2
B2tE(V)J N i

where e(p) gives the energy distribution of the incoming radiation. If the energy differ­
ence E2 - E i is sufficiently small, so that the ratio hv/kT is very small (as occurs, for
example, in the microwave region at room temperature), Eq. (13.22) shows A 2\/B2iV.(v)
to be negligible compared with unity.

F X.

rW V W rV W W
rV V V W rW V W
IlP hv hv rW V W

Ni 1 x

<«) (b)
Fig. 13-7. Basic operational principle of lasers and masers.
13.6) The photon gas 535

In this case, we may write

Emission rate V2
Absorption rate Vi

If the substance is in thermal equilibrium, V 2 is smaller than .Vi and the emission rate
is also smaller than the absorption rate. But if, by some means, the relative population
of the excited and ground levels is inverted, so that N 2 is larger than V i, making the
ratio V 2/ V 1 larger than I, then the emission rate is larger than the absorption rate. In
other words, if radiation of energy density e(v) passes through this system, the radiation
that comes out has more photons of frequency v than the incident radiation |Fig. 13—7(b)],
resulting in an “amplification” of the radiation at that frequency. This is only true, of
course, if £2 — Vi = hv. Since more atoms are de-excited than excited, the upper level
begins to be depleted, so that the amplification is decreased until thermal equilibrium is
re-established. Thus, to sustain a constant amplification, it is necessary to continuously
replenish the atoms in the upper level or to remove atoms from the lower level by some
Other means. The devices in which this is done are called masers and lasers. These are
coined words, acronyms for “ Microwave Amplification by Stimulated Emission of Radia­
tion” and “ Light Amplification by Stimulated Emission of Radiation,” depending on the
region of the electromagnetic spectrum in which they act.

Kxcitcd state

M eta sta b le state

(u pper laser lev e l)

Optical
pumping

/ G rountl state
(lo w e r laser le v e l)

Fig. 13-8. Three-level laser.

Several means have been devised to overpopulate the upper level in a steady fashion.
AU these methods require some expenditure of energy, and the efficiency of a maser or
laser is the ratio between the energy output and the energy input. One typical method is
optical pumping, in which energy is supplied, either continuously or in bursts, in great
quantities simply to excite the system to higher energies. As the system returns to the
ground state, some excited atoms decay into states which are metastable, and these
states may easily become highly populated relative to some lower state, as shown in
Fig. 13-8. Stimulating radiation of frequency v = (V 2 — Ei)/h will then give the de­
sired amplification.
Masers and lasers are very useful because they produce a very intense beam of co­
herent, monochromatic radiation. The student should recall that when several sources
radiate in phase (or coherently), the resultant amplitude is the sum of the individual
536 Quantum statistics (13.7

amplitudes. If all sources are identical, we have

Resultant coherent amplitude = N X source amplitude,

where N is the number of sources. Since the intensity of the source is proportional to
the square of the amplitude, we have that

Resultant coherent intensity = N 2 X source intensity.

If the number of sources is large, the stimulated radiation may be very intense. On the
other hand, if the sources radiate incoherently, the individual intensities add linearly;
that is,
Resultant incoherent intensity' = N X source intensity.

Therefore, in masers and lasers the stimulated, coherent, monochromatic radiation is

very intense, in comparison with the spontaneous incoherent radiation, which is called
noise in these devices. Due to the strong predominance of induced transitions, the noise
is relatively smaller in masers and lasers than in conventional amplifiers and oscillators.
Mascr amplifiers are used whenever very' low noise is of prime importance, such as in
radioastronomical work, satellite communications, and microwave spectrometry.

I It.7 Ilv a t Vapavitfi o f Soiids

As explained in Chapter 0, solids are regular aggregates of large numbers of atom s
(or m olecules) held in their positions of fixed equilibrium by strong cohesive forces
resulting from their electrical interactions. The only individual m otions o f the
atom s are small vibrations around their equilibrium positions. B u t the coupling
between atoms is so strong that you cannot set one atom in vibration without dis­
turbing the nearby atoms, and eventually the whole solid. Therefore we must
consider collective vibrational excitations of the solid, similar to those which were
considered in Exam ple 6.2 for a linear lattice.
These collective vibrations set up standing waves in the solid. Tlieir frequencies
depend on the shape and size of the body, and in a way' are similar to standing
w aves in a cavity. Although the possible frequencies have a discrete spectrum,
their spacing is very small if the body is relatively large compared with atom ic
dimensions and the spectrum may be assumed to be continuous. These standing
waves have the same nature as elastic waves propagated through a solid, and
therefore their propagation velocity is the same as the velocity of the elastic waves,
also called the v e lo c i t y o f s o u n d .
There are tw o kinds of elastic waves in a solid: longitudinal and transverse.
T h ey propagate with velocities Vi and V1, respectively. T o obtain the number of
different m odes of vibration in the frequency range between v and v - f d v , ex­
pressed as g ( v ) d v , we must count the longitudinal and the transverse modes
separately. Thus for transverse w aves we have, using E q. (13.18) with c replaced
hy v t ,
g ,( v ) d v = V2 d v ,
vf
13.7) Heal capacity of solids 537

while for longitudinal waves, which have one degree o f freedom, the modes of
vibration are one-half as m any:

g t(v ) dv = V2 dv.
v3
i

In each expression we use the velocities of propagation i>i and v,, corresponding to
longitudinal and transverse waves, respectively. T h e total num ber of vibrational
modes in the frequency range dv is then

g (v ) dv = g , ( v ) dv + g,(v) dv — 4 irV v2 dv. (13.23)

V ; Vt /

In a continuous medium there is no limit to the total number of vibrational modes.

But in a solid, which has an atom ic structure and contains N atoms, any vibra­
tional m ode must be described in terms of the S N positional coordinates of the
atoms. This therefore imposes a lim it on the Iolal number of independent modes
of freedom , which must be equal to SN. T his in turn imposes a limit on the maxi­
mum vibrational frequency because we must have, using E q. (13.23),

SN = g (v ) dv = 4 icV + J q 1/2 dv

or

S N = A ttV 0 + j > (13.24)

which determines the cutoff frequency V0- (T h e existence of a cutoff frequency in

the vibrations of a crystal lattice was discussed in Exam ple 6.2.) Using Eq. (13.24),
we m ay write Eq. (13.23) in the form

g{v) dv = ~ V2 dv. (13.25)

T h e problem we r re discussing here is very similar to that o f standing electro­

magnetic waves in a cavity. T h at discussion gave rise to the concept of a photon
gas introduced in Section 13.6 for analyzing blackbody radiation. W e may thus
associate with the vibrational modes of the solid, which of necessity are quan­
tized, a phonon gas com posed of “particles” or phonons of energy hv. T h e concept
of phonon was introduced in Exam ple 6.2. Since all phonons are identical and
since there is no limit to the number of phonons in the same energy state, we may
expect that phonons in thermal equilibrium obey Bose-Einstein statistics. Also
the number of phonons is not fixed, since their number may increase or decrease
depending on whether the energy o f the modes o f vibration is increased or decreased.
Thus we must use Eq. (13.15), setting a = 0, as we previously did for the photon
gas, and replace </,· by g(v) dv, given b y E q. (13.25). T h e number of phonons of
energy E — Iiv in the frequency range between v and v + dv and in thermal
538 Quantum statistics ( 13.7

TABLE 13-3 Dchye Temperatures of Some Solids

Substance e D, 0K Substance θ ο, 0K

Ag 225 Ge 366
Au 165 Na 159
C (diamond) 1860 Ni 456
Cu 339 Pt 229

equilibrium with the solid lattice at temperature T is then

g (v) dv 9N V2 dv
dn =
ek r,k r - I V3
0 Ck r lk r - I

T h e total vibrational energy o f the solid in the frequency range dv is

9Nh V3 dv
d U = Iiv dn =
V3
0 ekrlk T - I

and the total vibrational energy o f the solid is

U = f 0Iivdn = ^ Γ —α / "
Jo "o Jo Chrlkr —I
W e should add to this energy the zero-point energy associated with each of the
modes of vibration. However, this energy is temperature independent and is of no
concern to us here. The heat capacity o f the solid at constant volum e is then

_ _ 1 (d U \ M aIi 2 Γ v V rlkT m 9 p .
Cv N \d T jy V30IcT 2 Jo (ehr' kT - I ) 2 ( }

It is convenient to define the Debye temperature 0 d as k&D = hv0 or

0 „ = hv0/k. (13.27)

T h e value o f Θ ρ for some solids is given in T able 13-3.

Recalling that kN a = R and setting x = Ιιν/kT, we may write Eq. (13.20) in
the simplified form

^=9β(έ)λ / 7' N3 [ °DlT ,V

(13·28)
T h e graph o f C v against T / (jn is indicated in Fig. 13-9. This theoretical curve
is follow ed in a surprisingly accurate way by most substances, as shown in the
figure by the experimental points.
13 .7 ) Ileal capacity of solids 539

Cv
It

Fig. 13-9. Heat capacity of a crystal lattice as a function of the temperature.

It may be noted that at temperatures of the order o f 0 d or larger, the heat

capacities o f all substances practically attain the value 3 R , a result called the
Dulom j-Pelil law, since it was first noticed experimentally by these men in the
nineteenth century. This is also in agreement with the principle o f equipartition
of energy, because for k T » hv0 = k&d, the vibrational energy per degree of
freedom should be 2 (\ k T ) = kT, and for the 3 degrees o f freedom of each atom,
3kT. Therefore

U = N (S k T ) = 3 k N T = S y R T ,

corresponding to C v = 3 R, in agreement with the D ulong-Petit law. O bviously

substances whose D ebye temperature is much higher than room temperature
deviate substantially from the D ulong-Petit law at such a temperature.
A t this point w e should consider whether, in the special case of metals, we
should take into account the energy of the free conduction electrons when we are
com puting the heat capacity Cv- W c must recall that free electrons follow Ferm i-
D irac statistics and that the equipartition of energy applies to them only at tem­
peratures for which k T » eF, where eF is their Fermi energy, or T » eF/fc = 0 F,
where 0 F is the Fermi temperature. But when we examine the values of eF and
0 F given in T able 13-1, we see that the Fermi temperature 0 F is so high that
only a few electrons are excited when the metal is heated at temperatures used
in laboratories and industry. Thus electrons contribute a negligible am ount to
the specific heat of metals. W e must note, however, that at very low tem pera­
tures, close to absolute zero, when C v is also very small, as seen in Fig. 13-9, the
electronic contribution to C v is relatively im portant. A t these temperatures
the very few electrons that are excited above the Fermi level e F contribute
to the internal energy an am ount larger than the energy of the collective lattice
vibrations.
5-tO Quanlum statistics ( 13.8

Ht.it T h v Itlval G a s in Ifuantum Statintivs

AU particles follow either Ferm i-D irac or Bose-Einsteiii statistics. Therefore even
an ideal gas should be analyzed from the point o f view of quantum statistics.
Let us first consider an ideal gas com posed of particles that follow Bose-Einstein
statistics (which is the m ost com m on situation because molecules have either zero
or integral spin). The number dn of molecules with energy between E and E + <IE
is given by E q. (13.15), with r/, replaced by

g (E ) dE = 47rF(^ 3- — E 112 dE,

which is E q. (10.39). Therefore

4ttF(2m3) 1' 2 E w dE
dn =
h3 ea + E lk T _ J

If we set x = E / k T and recall Eq. (10.40) for the partition function of an ideal
gas, 7, = V (‘2 nnikT)'il2/li3, we obtain the total num ber of molecules as

N = 2 Z f _x^_dx_ (1 3 2 9 )
V t t do ea+z — I

Recalling that in Bose-Einstein statistics a is positive, we have

(c“ + I - I ) " 1 = <Γα- ' ( 1 - e~a~x) ~ l = e~a(e ~ x + β~α~ 2χ + · · ■),

and substitution into Eq. (13.29) gives us

κ=ζ’-{'+φ-,
A s a first approxim ation, we m ay write e~a = N / Z , which is the same result we
obtained in Section 10.3. As a second approximation we m ay write

= + ^ 5 C -" + - - ) I+"')-
(13.30)

which allows us to obtain a as a function of N and T. The total energy of the gas is

U = Γ —
dx
13.8) The ideal gas in quantum statistics 541

In t r o d u c in g th e v a lu e o f e “ as g iv e n b y E q . (1 3 .3 0 ), w e fin a lly o b ta in

(1 3.31 )

W h e n w e c o m p a r e th is w i t h th e c la s sic a l o r M a x w e ll- B o ltz m a n n id ea l-g a s result,

U = §fciV 7', w e s ee th a t th e q u a n tu m e ffe c t in B o s e -E in s tc in s ta tis tic s decreases
th e e n e r g y o f th e gas.
T h e p res s u re o f th e ga s (s e e E x a m p le 13.7) can b e s h o w n to b e

(1 3.32 )

a n d th u s w e s ee th a t, in B o s e - E in s t e in s ta tis tic s , th e p ressu re o f a n id ea l ga s is

a ls o less th a n th e p ressu re o f a c lassical ( o r M a x w e ll- B o ltz m a n n ) id ea l gas.
T h e d e p a r t u r e o f a q u a n tu m id e a l gas fro m a classical id ea l ga s is c a lle d gas
degeneration ( “ d e g e n e r a t io n ” as used h ere h as no re la tio n t o th e d e g e n e ra c y o f
q u a n tu m s ta t e s ). O b s e r v in g th a t N /Z is p r o p o r t io n a l to ( N / V ) T ~ 3/2, w e re a lize
t h a t th e d e g e n e r a tio n o f a ga s b e c o m e s m o re im p o r ta n t a t lo w te m p e r a tu re an d h igh
d e n s ity , c o n d itio n s w h ic h o c c u r n e a r th e c o n d e n s a tio n p o in t. F o r m o s t gases a t
S T P , w e h a v e th a t N /Z is o f th e o r d e r of· IO - 5 , an d th e re fo re ga s d e g e n e r a tio n is
n e g lig ib le , s h o w in g th a t M a x w e ll- B o lt z m a n n s ta tis tic s can b e used s a fe ly in such
gases.
T h e t w o lig h te s t ga ses th a t fo llo w B o s e -E in s te in s ta tis tic s are I I 2 an d h eliu m .
F o r H 2 a t its n o r m a l b o ilin g p o in t, 2 0 .4 °Iv, th e v a lu e o f N /Z is 0.84 X IO - 2 , and
fo r h e liu m a t 4 .‘2 ° K , th e v a lu e o f N/Z is 0.139. T h u s h eliu m is a gas in w h ich
d e g e n e r a tio n s h o u ld p ro d u c e o b s e r v a b le e ffe c ts . I n fa c t, s o m e p ec u lia r b e h a v io r
o f h e liu m in its c o n d e n s e d p h a se, k n o w n as H e - I I , has been a scrib ed to c o m p le te
B o s e -E in s t e in d e g e n e r a tio n .
I n th e ca s e o f an id e a l ga s t h a t fo llo w s F e r m i- D ir a c s ta tistics (su ch as m o n ­
a t o m ic h y d r o g e n ), th e re s u lts a r e q u ite s im ila r. H o w e v e r , w e re c a ll th a t in F e rm i-
D ir a c s ta t is t ic s a m a y b e e ith e r n e g a tiv e o r p o s itiv e , a n d th e r e fo r e th e cases
a > 0 and a < 0 m u s t b e tr e a te d s e p a r a te ly . W e sh a ll n o t e la b o r a te fu r th e r on
th is case. W e p o in t o u t, h o w e v e r , t h a t a lth o u g h th e p ressu re a t th e a b s o lu te ze ro
o f an id e a l g a s t h a t fo llo w s e ith e r A la x w c ll- B o lt z m a n n o r B o s e -E in s te in sta tistics
is z e ro , th e p re s s u re o f an id e a l g a s t h a t fo llo w s F e r m i- D ir a c s ta tis tic s a p p ro a ch es
a fin it e v a lu e n e a r th e a b s o lu te z e r o ; i.e., th e r e is a z e ro -p o in t p ressure. T h e re a ­
son f o r th is is th a t, e v e n a t a b s o lu te ze ro , an a s s e m b ly o f fe rm io n s has a z e ro -p o in t
en ergy U = f j V « f (s e e E x a m p le 13.2). R e c a llin g E q . (1 1 .3 7 ),

dU = T d S - p dV

w e h a v e , w h e n th e e n t r o p y is c o n s ta n t, dUs = — P dFs· H ence

(13.33)
542 Quantum statistics (13.8

T h e r e fo r e th e z e ro -p o in t p ressu re o f a s y s te m o f ferm io n s is

P=-(W)s=-^w /d U \ 3 , r dep

B u t fr o m E q . (1 3 .1 0 ), w e h a v e In tp = — § In V -f- C ; h en ce d tp /d V = — 2ty/'.W .
T h is g iv e s

2 N tv
P = I f (1 3.34 )

fo r th e z e ro -p o in t p ressure o f a F e r m i- D ir a c gas.

E X A M P L E 13.7. Pressure o f an ideal gas in terms o f the internal energy and the
volum e.

S olution: W c recall that, according to E q . (13.33), the pressure of a system o f particles

m ay be com puted b y p = — (dU /dV)s- But U = 2 , n,£\. N o w in a process at con­
stant en tropy, the occupation numbers n, must remain constant since, as explained in
Section 11.9, a change in en tropy (or heat absorption) is associated w ith a change in the
n.’s. H ence ( d U /d V )s = Σ * Tii(QEiZdV)l and

p = — Ei n ‘ w ’ (1335)
Assum ing th at the ideal gas is composed o f noninteracting particles in a cubical box of
side a and volu m e V = a:i, the en ergy levels are given b y E q. (2.17),

2 o
„ T fl~ 2 , 2 , 2. TC h 2 2 2,
Li = 2^T* (Sl + N' 2 + N a ) = 2m VW (X1 + N’2 + Na)’
which gives
2 ■>
SEi 2 τ h~ . 2 . 2 , .2. 2 Ei
dV ~ 3 2mFS/3 Nl N’2 _ 3 V '

Substituting this result in E q. (13.35), we find, for the pressure o f the system o f non­
interacting particles,

P = I z f H f <1 3 ·3 6 )
I

F o r an ideal gas which follows M axw ell-B oltzm an n statistics, we have U = ik N T , and
hence p = k N T /V , in agreem ent w ith E q . (11.16). F o r a Bose-Einstcin ideal gas, we
must use E q. (13.31) for U, obtain in g the result p reviously stated in E q. (13.32) for p.
F o r a F erm i-D ira c ideal gas a t absolute zero, U = %Nir and p = f .V ir / F , which is the
value given in E q . (13.34). A t tem peratures differen t from absolute zero, the pressure
depends on the sign o f a. F o r p ositive a, which holds norm ally at v e ry high tem pera­
tures, the pressure o f a F crm i-D irac ideal gas is

EV 7’ / I AT \
P Y 25/2 2, )
13.9) Comparison of the Ihree statistics 5'i3

and hence is sligh tly larger than the classical ideal-gas pressure. F o r negative a, which
holds for low temperatures, the pressure is

2 V eF[ 5 tV m \ 2 I
" - 5 — + - · · · ■

11t.it Iom pariMHn o f Iliv T h rv v Slnlistivs

In th e p re v io u s s ec tio n w e sa w th a t q u a n tu m e ffe c ts a re r e la t iv e ly s m a ll in id ea l
gases a t lo w c o n c e n tra tio n a n d h igh te m p era tu re s. W e shall n o w c o m p a re th e
th re e s ta tis tic s to d e te rm in e th e e x t e n t to w h ic h th e y g iv e c o m p a ra b le resu lts.
R e c a llin g E q s . (1 0 .9 ), (1 3 .5 ), an d (1 3 .1 4 ), th a t is,

(a ) M a x w e ll B o ltz m a n n , n,· = giC~a~ E ',kT,

( b ) F e r m i- D ir a c , m = - ,
c * -F I

( c ) B o s c -E in s te in 1 n,- = 9' ----------,

c _ j

w e see th a t th e th re e can b e w r itte n in th e fo rm

S i - F «5 =
m

w h e re 5 = 0 fo r M a x w e ll- B o ltz m a n n , — I fo r F e rm i-D ira c , a n d + 1 fo r B o s e -

E in s te in sta tistics. W e can c le a rly see th a t if </,·/?!; » I o r if n j « th a t is, fo r
d ilu te d system s, th en th e th re e s ta tistics g iv e p ra c tic a lly id e n tic a l results. T h is
is tru e a t h ig h te m p e ra tu re s (b ec a u se o f th e in crea se o f « w it h te m p e r a tu re ).
T h e r e fo r e , except a t v e ry lo w te m p e r a tu re , w e m a y n e g le c t m o s t q u a n tu m -
s ta tis tic a l effec ts . T h is ju s tifie s th e use o f M a x w e ll- B o ltz m a n n s ta tis tic s in m a n y
instances.

Itv fvrv n v vs
1. “ T herm odyn am ics and Quanta in P lan ck’ s W o rk ,” M . K lein , Physics Today, N o v e m ­
ber 1966, page 23
2. “E vo lu tio n of Masers and Lasers,” B. L en gyel, A m . J. Phys. 34, 903 (1966)
3. “ Resource L e tte r M O P - I on M asers and on O ptical P u m p in g," H . M oos, A m . J. Phys.
32, 589 (1964)
4. Statistical Thermodynamics, E. Schrodinger. C am bridge: C am bridge U n iversity
Press, 1964, C h apter 13
5. Statistical Physics, CL W annier. N e w Y o r k : John W iley , 1966,P art I
6 . Fundamentals o f Statistical Thermodynamics, R. Sonntag and G. Van W ylen . N ew
Y o r k : John W iley , 1966, Chapters 7, 8 , and 11
7. The Feynm an Lectures in Physics, Volum e I, It. Feynm an, It. Leigh ton , and M . Sands.
R eading, M ass.: Addison-W esley, 1963, Chapters 41 and 42
Wt Quantum statistics

P ro M vn ts

13.1 T h e Ferm i energy varies with the 13.7 P lo t the Richardson-Dushm an equa­
tem perature according to the expression tion for therm ionic emission as a function
of kT/at>. Show th at the tem peratu re at
which therm ionic emission is m axim um is
T = e<f>/'2k. E stim ate the value o f this
tem perature for some o f the metals given
where tp is the value at Τ' = 0 , given in in T a b le 13-2.
T a b le 13-1. Show that the corrective term
13.8 W h en M axw ell-B oltzm an n statistics
corresponds to a change o f 1 % in the Ferm i
is used instead o f F erm i-D irac statistics to
energy at a tem perature 7’ = V 3 θκ/5ττ.
analyze therm ionic current density, the
E stim ate this tem perature for some o f the
expression obtained is
metals given in T a b le 13-1 and conclude
to what exten t one can assume th a t the j = A T U2e~'*!kT.
Ferm i energy remains constant between
absolute zero and room temperature. (a ) D e riv e this equation, (b ) P l o t j against
kT/e4> and com pare with the p lo t o f the
13.2 Find the average v e lo c ity and the
Richardson-Dushman equation, assuming
average energy o f electrons a t 0 ° K in a
in both cases that φ = 3 eV . (c ) E stim ate
m etal having IO 22 electrons per cm 3.
the tem perature H = ίφ/ k for some metals
13.3 Show that the number o f ferm ions and decide whether both equations give
w ith a v elo c ity betw een v and v + dv at a clearly distinguishable results at room
tem perature T is temperatures.

13.9 Show that the constant A in E q .

dN = 8 rrFm 3 V2_________ (13.11) has the theoretical value of 120 Λ
ft3 ! C m - 2 oK - 2.

13.10 From our discussion o f the poten­

13.4 Show that the number o f ferm ions tial step in Chapter 2, we know th at some
w ith a v elo c ity whose com ponents arc be­
electrons that reach the surface o f a metal
tween vx and vz + dvz, t>„ and v„ - f dvy, and should be reflected back in to the metal
v, and Vg -f- dvx is even if their energy is larger than cφ. (a)
M o d ify E q. (13.10) to take this effect into
_ 2 vVm dvxdvy dvx. account. J ustify the fact that the experi­
1 ~ , 3 e (m .* / 2 - .f ) l k T + j ' mental values for A (T a b le 13-2) are less
than the theoretical value given in the
13.5 Show th at the number o f ferm ions previous problem, (b ) Find the reflection
w ith a com ponent o f v elo c ity along the X- coefficient for cesium and chromium.
axis between vx and vx -f- dvx is 13.11 F o r what values o f the energy E,
2 greater than ep, is n, = gie~us~,t >lkT
within 10% o f E q . (13.5)?
1 = h 3k f - ln Ie + 1I ώ ·
13.12 F o r the energies indicated in Prob­
lem 13.11, w e can write
[Hint: Use the integral JJ5 ( ae1 + I ) -1 dx =
In ( I + 1/a).]
N (E ) dE - 8xV(2™3)112 E m c- iS - .F)ikT
13.6 Using the result o f Problem 13.5, de­
rive Richardson’s equation (13.11). [Hint:
Use the approxim ation In ( I -f- x) = x, instead o f E q. (13.9). Show th at the num­
when x is small.] ber o f electrons per unit volu m e with
 Problems 545

energies e<|ual to or greater than a certain expression for the heat capacity is
value Eo larger than e? is
Cy = ψ Ι ϊ π ( Τ / θ D) \
8 t 1 '( 2 » i ) e.F/kTkT
T h e dependence o f Cy on T3 a t low tem ­
1/2 I . E0 .-,1/2 - K 0IkT peratures has been verified experim entally.
X [(irkT) ho e [Hint: Set x = ©d/ T in E q. (13.28) and
2 “ 6 Γ ίΪ Γ
note that the upper lim it can be equated
[Hint: Refer to Problem 10.21.] to infinity.]
13.13 Using the result o f Problem 13.12, 13.20 From the follow in g experim ental
find, for a metal w ith « f = 2.00 e V and d ata for nickel and silver, determ ine the
φ = 3.00 eV, the ratio o f the number of D eb ye tem perature o f the tw o materials.
electrons per unit volum e having an energy T h e atom ic masses are 59 and 108 and the
equal to or larger than the work function densities are 8.9 X IO 3 kg m - 3 and 1.05 X
a t room temperature to the number at IO4 kg m - 3 , respectively.
IOOO0K . [Ilinl: See Problem 13.11.]
13.14 Find the number o f photons per
T, “K C r, cal m ole 10 K 1
cubic meter having a frequency between
^mnx and I.OSvmnx in a blackbody radiation Ni Ag
field at. 3O0°K, where v,„„x corresponds to
the peak energy density. 2 0.0041 0.00013
13.15 Assume th at photons behave as 4 0.0080 0.0024
classical oscillators with an average energy 6 0.0132 0.0089
o f kT. Obtain the energy density distribu­ 8 0.0186 0.0242
tion; this is the Rayleigh-Jeans law, which 10 0.0238 0.0478
was mentioned in Problem 1.9. W h y does 12 0.0304 0.0830
this assumption g iv e the same energy dis­ 14 0.0379 0.134
tribution when w e make the low -frequency 16 0.0483 0.201
approxim ation of P lan ck ’s radiation law?
13.16 Assume that photons o b ey M axw ell- 13.21 Using the graph in Fig. 13-9, esti­
Roltzm ann statistics. Obtain the energy m ate the heat capacity at room tem pera­
density distribution. T h is is the W ien law, ture o f (a ) sodium, (b ) gold, (c ) copper, and
which was mentioned in Problem 1.9. W h y (d ) diam ond. Com pare with the experi­
does this assumption g iv e the same energy m ental values.
distribution when we make the high-
13.22 (a ) Consider a system composed
frequency approxim ation o f P lan ck’s radi­
o f .V harm onic oscillators of frequency v,
ation law ?
follow in g M axw ell-B oltzm an n statistics.
13.17 Using T a b le 13-3, find the maxi­
Find the heat capacity o f the system at
mum frequency and m inimum wavelength
constant volume. (b ) T his model was
for phonons in germanium and diamond.
used b y Einstein in the first attem p t to
Com pare with the w avelength o f neutrons
a p p ly statistical methods to explain the
at room temperature (3 0 0 °K ).
h eat capacity of solids. Introducing the
13.IS Find the ratio o f spontaneous emis­ constant ©b = hv/k, express Cv in terms
sion probability to induced emission prob­ o f © e /T . Com pare with the expression
a b ility at 300°K for (a ) the m icrow ave for Cv in the D ebye theory. A n a lyze the
region, v κ IO 13 IIz , and (b ) the optical w a y that the theories can be differentiated.
region, v ~ IO la H z. [.Vote.- E instein’s theory was discarded be­
13.19 Show th at at tem peratures very cause o f the fact that it was im possible to
small compared w ith ©n, the D eb ye find a value o f © e for each substance th at
546 Quanlum statistics

would give results in agreem ent w ith exper­ 13.27 E stim ate the value o f N /Z for Ni
im en t a t both high and low temperatures.] at S T P , where Z is the classical partition
13.23 Show that the heat capacity at con­ function. D eterm ine the relative effect
stant volu m e o f an ideal Bose-Einstein gas o f the gas degeneration term in expression
is given b y (13.32) for the pressure o f a Bose-Einstein
gas. A lso determ ine the effect 011 the heat
capacity o f this gas (giv en in Problem
Cv = iR 13.23).
13.28 E stim ate the zero-point pressure o f
J _ IN the electron gas in a metal. In v iew o f the
' 35/2
value obtained, explain how the electrons
remain inside the metal.
where Z is given b y E q. (10.38). E stim ate
the effect o f gas degeneration 011 the heat 13.29 Show th at the en tro p y o f a system
c ap acity of helium at room tem perature o f particles in quantum statistics is given

and at I atm o f pressure. by

13.24 Show that the heat capacity at

U
constant volu m e o f an ideal Ferm i-D irac S = -ψ + akN
gas is given b y
± kY g . In (I ± e~a- BilkT),

where the p ositive (n eg a tiv e ) sign corre­

From this result estim ate the heat capacity sponds to Ferm i-D irac (B ose-E in stein )
due to free electrons in a metal. V e rify th at, statistics. A lso show th at in both cases if
except at v e ry low tem peratures, the elec­ ot is v ery small the expression for S reduces
tronic heat cap acity is negligible com pared to E q . (11.28). Hint: F irst show, using
w ith the lattice heat capacity as given by either E q . (13.3) or (13.13), that
the D eb ye theory.
13.25 Show that the tem perature
which the lattice and the electronic heat
capacities are equal is
at In P = Y ± 9.
('^M1
1/2
T0 = (5θ£/24ΐΓ 0 F)

E stim ate this tem perature for some metals. 13.30 In quantum statistics the p artition
Show that at tem peratures low er than T0 function is defined as
the electronic heat capacity is larger than
—a —E | / kT 1
the lattice heat capacity, while the reverse Z11 = ± Y (ji In (I ± c
is true for tem peratures higher than T0.
[Hint: Use the result o f Problem s 13.19
where the p ositive (n eg a tiv e ) srgn refers
and 13.24.]
to Fcrm i-D irac (Bose-E in stein ) statistics.
13.26 From the expression given in P ro b ­
Show th at the total number o f particles,
lem 13.24 for the heat capacity o f an ideal
the total energy, and the en tropv are given
F erm i-D irac gas, show that the entropy of
by
the gas, when cy/kT « I, is
N = - ib Z J d c t ) τ,
S = (.V R i c 2/ 2 ) (k T / t y ) V = k T 2(d Z ,/d T )0,
X [I - ( τ 2/ 1 0 )(Λ Γ / ίρ )2 + · · · ] . S = k T (d Z ,/d T )a + akX kZ„
 Problems 547

[Hint: F o r the last relation, see the expres­ relations reduce to E q. (10.24) and E q.
sion for S given in Problem 13.29.] (11.28), respectively.
13.31 Show that, when a is v e ry small, 13.32 Show th at the p artition function o f
Zq = e~aZ, where Zq is the quantum a photon gas is Z - ( 8 τ 5 V/ 45)(k T /he)3.
partition function defined in Problem 13.30 T hen show th at the total energy o f a photon
and Z is the classical partition function gas is U= ( 87t5F / 15) (kT )* /(he)3 and
defined in E q . (10.22). Show also that the that the entropy is S = 4C//37\ [Hint:
first relation in Problem 13.30 reduces to N o te th at Jq0 x - In (I — e~x) dx = — jr4/15;
an id en tity, while the second and third use the relations given in Problem 13.30.]
A PPE N D IX E S
 A P P E N D IX
SUPPLEM ENTARY NOTES

I. IlelativiHtiv M ec h a n ic s
L e t us c o n s id e r tw o in e r tia l o b s e rve rs , 0 a n d O ', in r e la t iv e m o tio n . G iv e n th a t v
is th e v e lo c it y o f 0 ' r e la t iv e to 0 , th en th e v e lo c it y o f 0 r e la t iv e to 0 ' is — v. We
shall o r ie n t th e axes XYZ an d X 'Y 'Z ' a tta c h e d t o 0 an d O ', re s p e c tiv e ly , so th a t
axes X an d X' are p a ra lle l to th e r e la t iv e v e lo c it y t> an d th e Y an d Y' axes are
p a ra lle l t o each o th e r. T h e n axes Z an d Z' are also p a ra llel (F ig . A - l ) .
S u p p o se th a t W hen 0 an d 0 ' are c o in c id e n t a lig h t sign a l is p ro d u ce d a t th e
c o m m o n o rig in . I f c is th e v e lo c it y o f lig h t in v a c u u m as m easu red b y 0 , a fte r a
tim e I o b s e r v e r O sees th a t th e w a v e fr o n t o f th e sign al is a sph ere o f ra d iu s r, so
th a t w h e n th e w a v e reach es p o in t A w e m u st h a v e r = Cl, o r since

r 2 = X2 + y 2 + z2,
th en
s2+ V2 + z 2 — C2J2 = 0. (A .I)

I t is a c c e p te d as a b asic p rin c ip le th a t th e v e lo c it y o f lig h t is th e s a m e fo r a ll

in e r tia l o b se rve rs . T h e e x p e rim e n ta l fo u n d a tio n o f th is assertion is b ased on th e

F ig . A - l . Fram es o f reference in uniform relative translational m otion.

551
552 Appendix

e x p e rim e n ts o f M ic h e ls o n an d M o r l e y 1 w h o m easu red th e v e lo c it y o f lig h t r e la t iv e

t o th e e a rth in d iffe r e n t d irec tio n s , an d fou n d th a t th e resu lt is th e sam e irresp ec­
t iv e o f th e d ire c tio n o f p ro p a g a tio n . T h e r e fo r e , i f o b s e rv e r 0' also m easu res th e
v e lo c it y o f lig h t as c in all d ire c tio n s (s o th a t to 0' th e w a v e fr o n t o f th e s ig n a l is
also a s p h e re ), h e m u st w rite , w h e n th e lig h t w a v e reach es p o in t A, th a t r' = C l' or

(A . 2 )

N o t e th a t o b s e rv e r 0' n o t o n ly m easures d iffe r e n t sp a ce c o o rd in a tes fo r p o in t A

fr o m th ose th a t O m easures fo r p o in t A, b u t fo r h im th e m easu red tim e o f a r r iv a l
o f th e lig h t s ig n a l at .4 is also d iffe r e n t fr o m th e tim e m easu red b y 0 . T h is is
r e q u ire d i f th e v e lo c it y o f ligh t is to be th e sam e fo r b oth o b servers.
T h e n e x t task is to o b ta in a tra n s fo rm a tio n r e la t in g th e q u a n titie s (x, y, z, I) and
(x', y ', z ', I ' ) m easu red b y 0 a n d 0 ' a n d g iv in g th e space d is p la c e m e n t a n d th e
tim e in te r v a l o f tw o e ve n ts , w h ich a re: ( I ) th e em ission o f a lig h t sig n a l w h en 0
an d 0 ' w e re c o in c id e n t, an d ( 2 ) its a r r iv a l at. A, w ith b o th sets o f q u a n titie s s a t­
is fy in g E q s . ( A . l ) an d ( A . 2 ), r e s p e c tiv e ly . T h e s y m m e tr y o f th e p ro b le m su ggests
th a t y' = y a n d z’ — z. A ls o , since 0 0 ' = vt fo r o b s e rv e r 0 , it m u s t b e th a t
x = vl fo r x' = 0 (p o in t O '). T h is su ggests th a t w e set x' - k(x — vl), w h e re k
is a c o n s ta n t to b e d e te rm in e d . S in ce I' is d iffe r e n t fro m I, w e m a y also iissuine th a t
I' = a(t — bx), w h e re a an d b are c o n s ta n ts to b e d e te rm in e d (f o r th e G a lile a n
tr a n s fo rm a tio n , k = a = I an d b= 0 ). M a k i n g a l l th e se s u b stitu tio n s i n E q . ( A . 2 ),
w e have
k 2(x 2 — 2vxt + V2I 2) y 2 -j- z2 = c2a2(t2 — 2bxt + b2x 2),

or, if w e c o lle c t term s,

T h is e q u a tio n , h o w e v e r, m u st be id e n tic a l w ith E q. ( A . l ) . T h e r e fo r e

k2 — b2a2c2 = I, k 2v — ba2c2 = 0 , a2 — k 2v2/ c 2 = I.

S o lv in g th ese th re e e q u a tio n s fo r k, a, a n d 5, w e h a v e

k = a = an d b = v /c 2. (A .3)
V I — v2/ c 2

H e n c e th e tra n s fo rm a tio n c o m p a tib le w ith th e in v a ria n c e o f th e v e lo c it y o f lig h t is

x' = (x — i'O / x / l — v 2/ c 2 ,

y' = y,
(A . 4)
z' = z,
t’ = (t - vx/c2) / V I - V 2Z c 2.
 Appendix 553

T h is s et o f re la tio n s is c a lle d th e Lorenlz transformation. B eca u se o f th e re la tio n ­

sh ip set u p b e tw e e n E q s . ( A . I ) an d ( A . 2 ), w e s a y th a t a L o r e n t z tra n s fo rm a tio n
le a v e s th e q u a d ra tic fo r m x 2 + y 2 + z2 — c2t2 = O in v a r ia n t w h en w e pass o v e r
to th e p rim e d c o o rd in a tes . T l i o L o r e n t z tra n s fo rm a tio n red u ces to th e G a lile a n
tr a n s fo rm a tio n w h en v« c.
If m0 is th e m ass o f a p a rtic le w h en it is at re st r e la t iv e to an o b s e rv e r, th e
m o m e n tu m o f th e p a rtic le w h en m o v in g w ith v e lo c it y v r e la t iv e to th e o b s e rv e r is

p = km 0v = m°V = mv, (A . 5 )
V l — v2/ c 2
w h e re
= k m 0 = O To/vT — V 2I c 2 (Λ . 0 )

Ls th e e ffe c t iv e m ass o f th e p a rtic le r e la t iv e to th e o b s e rve r. E x p re ss io n (A . 5 ) re ­

duces t o th e n o n r e la tiv is tic e xp ressio n fo r m o m e n tu m w h en v« c.
T h e fo r c e on a p a rtic le is d e fin e d as

V I — v2/ c 2

To c o m jiu te th e k in e tic e n e rg y o f a p a rtic le , w e re ca ll th a t v — d r/d l an d

v ■ dv — v dv. Then

= f"r.d ( m °V -Y
Jo \y/ 1 — v2/ c 2/

In t e g r a t in g b y p arts, w e h a v e

m qV2 I mow dv
Ek =
V l - v2/ c 2 Jo V l — V2I c 2
2 ___________________________ ^_______ ___________

+ m ocV l - m0c 2
V2I e 2 -----------
V l - V2I c 2

C o m b in in g th e firs t tw o te rm s w ith a c o m m o n d en o m in a to r, w e m a y w r ite

Ek = _ - — W 0C2 = (m — m0)c2. (A . 7 )
V l — V2I c 2

T h e r e fo r e w e m a y s a y th a t, as a resu lt o f th e d ep en d en c e o f th e m ass on th e v e lo c ­
i t y a c c o r d in g to E q . (A .G ), th e ga in in k in e tic e n e r g y o f a p a rtic le m a y b e con sidered
as a ga in in mass, Am = m — mn. W e can e x te n d th is in te rp re ta tio n to associate
554 Appendix

a c h a n g e in m ass A m to a n y c h a n ge in e n e rg y AEof a s y stem o f p a rticles. B o th

c h a n ges are re la te d b y th e exp ressio n

A E = (Am)C2. (A .8)

T h e q u a n t it y m 0c 2 is ca lle d th e rest energy o f th e p a rticle , an d th e q u a n tit y

E = E k + m0c2 = . m°C~- ■= m e2 (A . 9 )
V l - V2Icii

is th e total energy o f th e p a rticle . T h e to ta l e n e rg y o f th e p a rtic le , as h ere.d e fin e d ,

in clu d es k in e tic e n e rg y an d re s t e n e rg y , but n o t p o te n tia l e n e rg y .
C o m b in in g E q s . ( A . 5 ) an d (A . 9 ), w e see th a t

» = Τ Γ · ( A . 10)

U s in g E q . ( A . 5 ) t o e lim in a te v in E q . ( A . 10), w e h a v e th a t

E = c V m2
0c2 + p 2. ( A . 11)

S in ce E k = E - m0c2 = c \ / m 2c2 + p 2 — m0c2, w h e n th e v e lo c it y is s m a ll c o m ­

p a re d w ith c (o r w h en p is s m a ll c o m p a re d w ith m0c), w e h a v e th a t

Ek = 2m O + » jmJ3ci2
S + ---' <A · 12)

w h ic h red u ces to th e n o n r e la tiv is tic fo r m u la Ek = p / 2 wi0 w h e n p « m 0c.

A n in te re s tin g sp ecia l case occu rs w h e n th e p a rtic le has z e ro rest m ass ( m0 = 0 ),
w h ich is th e case fo r th e p h o to n an d th e n eu trin o . T h e n E q . (A . 11 ) red u ces to

E = cp or p = E /c . (A . 13)

T h is resu lt, su b stitu ted in E q . ( A . 10), g iv e s v = c. H e n c e a p a rtic le w ith ze ro

re s t m ass can m o v e o n ly w ith th e v e lo c it y o f lig h t an d can n e v e r b e a t re st in an
in e r tia l s ystem .
E q u a tio n ( A . 1 1 ) m a y also be w r itte n in th e fo rm

p2 — En 2//c 2 = — m0c
2 2
.

S in ce p is a v e c to r q u a n tity , w ith c o m p o n en ts pxi p y, pz r e la t iv e to th e XYZ fra m e

used b y o b s e r v e r 0 , w e m a y w r ite in stea d

Px2 + P l + p i - E 2Zc2 = - m ic2. (A . 14)

R e la t iv e to a n o th e r o b s e rv e r O' m o v in g w ith v e lo c it y v re la tiv e to 0, w e m u st h a v e

p i? + P i? + p i? - E l2I c 2 = - m2
0c2. (A . 15)
 Appendix 555

T h e s im ila r it y o f Eqs. ( A . 14) an d ( A . 15) to E q s . ( A . l ) an d ( A . 2 ) su ggests th a t w e

can m a k e th e correspon den ce

Vx -**> P i,- * ϋ< Pi cl -* E /c

in th e L o r e n t z tra n sfo rm a tio n (A .4 ) for th e space co o rd in a tes an d th e tim e in

o rd e r to o b ta in th e tra n sfo rm a tio n o f m om en tu m an d e n e r g y ; th a t is,

p i· = (Px — vE / c 2) / V I — v2/ c 2,
Pti' — Pui
( A . 16)
P i- = Pu
E' = (E - vpz) / V I - V2Jc2.

I f w e have a system o f noninteracting particles, we m ay w r ite the total m om en­

tum o f the Sj7Stem as P = Σ , p , and the total energy as

E — ^2 m i°2 — M c2,
i

w h e re M = m,·. A lth o u g h in re la tiv is tic d y n a m ic s it is im p o ss ib le to d efin e

th e c e n te r o f mass, w e m a y s till d efin e a c e n te r-o f-m a s s -v e lo c ity o r s y stem v e lo c ity
vc a c c o r d in g to E q . (A . 10), b y

vc = c2P / E = P /M . (A . 17)

In a fra m e o f referen ce m o v in g r e la t iv e to 0 w ith a v e lo c it y vc, th e to t a l m o m e n ­

tu m o f th e s y s te m is z e ro (th is is ca lled th e ze ro -m o m e n tu m o r C - fr a m e o f re fe r­
e n c e ). T h is sta tem en t can b e p ro v e d as fo llo w s : S u p pose that, o b s e rv e r 0 ' m o v e s
w ith v e lo c it y v re la tiv e to 0 in a d ire c tio n p a ra llel to P. T h e n a c c o r d in g to o u r
c o n v e n tio n in choosing th e c o o rd in a te axes, w e h a v e th a t Pz — P, P u = P . = 0
an d P z, = P ', P u, = P z, = 0. H e n c e th e first re la tio n in E q . ( A . 16) g iv e s

P' = k{P - v E /c 2). ( A . 18)

I f o b s e rv e r 0' is in the C -fra m e, h e m u st h a v e P' = 0. T h is req u ires th a t v = C2P / E ,

w h ic h is eq u a l to the v e lo c it y vc d e fin e d in E q . ( A . 17).

Mt. IolIisions
I n an is o la te d system o f p a rticle s (i.e ., a s y stem o f p a rticle s n o t s u b je c t to a n y
e x te r n a l a c tio n s o r forces), th e to ta l m o m en tu m an d th e to ta l e n e rg y , b o th re fe rre d
to an in e r tia l fra m e of refe re n ce , re m a in con sta n t. T h e s e tw o c o n s e rv a tio n la w s are
n o t in d e p e n d e n t because, in v ie w o f th e L o r e n tz tra n s fo rm a tio n (A . 16) fo r e n e rg y
an d m o m e n tu m , th e c o n s e rv a tio n o f m o m en tu m in all in ertia l fra m e s also req u ires
th e c o n s e r v a tio n o f en e rgy . W e sh all n ow a p p ly th ese c o n s e rv a tio n la w s to th e
an a lysis o f collision s.
556 Appendix

W h e n tw o p a rtic le s ap p ro a c h e acli o th e r, th e ir m u tu a l in te ra c tio n c h a n ges th e ir

m o tio n , p ro d u c in g an e x c h a n ge o f m o m e n tu m an d e n e rg y . W e th en s a y t h a t th e re
has b een a collision. In s o m e collision s (su ch as in n u clea r a n d c h e m ic a l r e a c tio n s )
th e fin a l p a rtic le s are n o t id en tic a l to th e in itia l ones. W h e n th e in itia l a n d final
p a rticle s are th e sam e, th e collis io n is c a lle d scatteriny.
In a c o llis io n e x p e rim e n t, w e u s u a lly k n o w p re c is e ly th e m o tio n o f th e p a rtic le s
b e fo re th e collisio n , since such m o tio n d e p e n d s on h o w th e e x p e r im e n t h as been
p rep a red . F o r e x a m p le, on e p a r t ic le m a y b e a p r o to n o r an e le c tro n a c c e le ra te d in
an e le c tro s ta tic a c c e le ra to r an d th e o th e r p a r tic le m a y b e an a to m p r a c tic a lly a t
rest in th e la b o ra to ry . T h e n w e o b s e rv e th e fin a l s ta te ; i.e., th e m o tio n o f th e tw o
p a rtic le s a t p o in ts fa r a w a y fro m th e re g io n in w h ich th e y c o llid e d (F ig . A - 2 ) . On
th e o th e r hand, if w e k n o w th e fo rc e s b e tw e e n th e p a rticles, w e m a y p r e d ic t th e
fin a l s ta te , so lo n g as w e k n o w th e in itia l s ta te . H e n c e th e an a lysis o f c o llis io n
e x p e rim e n ts p ro v id e s v a lu a b le in fo r m a tio n a b o u t th e in te ra c tio n b etw e en th e c o l­
lid in g p articles. T h is is o n e o f th e reason s w h y collis io n e x p e rim e n ts are so in te r­
e s tin g to th e p h y sic ist.
S in ce o n ly in te rn a l forces e n te r in to p la y in th e collisio n , b o th th e m o m e n tu m
an d th e to t a l e n e r g y are c o n s erve d . Let p \ an d /J2 b e th e m o m e n tu m o f each
p a rtic le b e fo re th e collisio n an d p[ an d p 2 b e th e m o m e n tu m a fte r th e c o llis io n .
C o n s e r v a tio n o f m o m e n tu m re q u ires th a t

P i + P 2 = p'l + P 2 ■ ( A . 19)

C o n s e r v a tio n o f e n e r g y re q u ires th a t

E1+ E2 = E \ + E 12, ( A . 2 0)

w h e re each e n e r g y is g iv e n b y E q . ( A . 11), s o th a t w e m a y w r ite

C V 7 W iC 2 + pi + c V 7 Vi2C2 + pi = c' V 7 m '2c2 + p '2 + c \ / m ' 2c2 + p 2 . ( A . 21)

B y p ro p e rly h a n d lin g E q s . (A . 19) an d ( A . 2 1 ), w e m a y fin d th e final m o m e n ta o f

th e p a rtic le s in te rm s o f th e in itia l ones. T h e a lg eb ra , h o w e v e r, in ge n era l is ra th e r
c o m p lic a te d .
R e c a llin g th a t E = E ic - f m0c2, w h e re Ek is th e k in e tic e n e rg y , in stea d o f E q .
( A . 2 0 ), w e m a y w r ite

Eki + m ic2 + Ek2 -f- Vi2C2 = E'ki + V i1

l C2 + E i2 + m2c2.

L e t us in tro d u c e a q u a n tit y Q d e fin ed as th e c h a n ge in k in e tic e n e r g y d u rin g th e

collis io n

Q = (.Ei I + E ( 2) — (E k i + E k 2) — ( n il + m 2 — m'i — w 2)c 2. (A .22)

T h e r e fo r e Q is also eq u a l to th e c h a n ge in re st e n e rg ie s d u rin g th e collisio n . If

Q = 0, k in e tic e n e rg y is c o n s e rv e d in th e collisio n , and th e collisio n is ca lled
clastic. W h en Q < 0, th e re is a d ecrea se in k in e tic e n e rg y (o r an in crease in m ass)
 Appendix 557

F ig . Λ - 2 . The to tal mom entum and F ig . A -3 . M om entum and energy are

the to tal energy arc conserved in all colli- conserved even if the number o f particles
sions. is not.

an d w e h a v e an inelastic collision of the first kind, also ca lled endoenjic. W h en

Q > 0, th e re is an in crease in k in e tic e n e rg y o f th e p a rticle s (o r a d ecrease in
m ass) an d w e h a v e an inelastic collision of the second kind, ca lled exoergic.
W h e n m o re th an tw o p a rticle s are p ro d u ced in a c o llisio n (F ig . A - 3 ) , th e a b o v e
d e fin itio n s b eco m e

Q — (ΣΖΑ^){ϊη&1 (ΣΖ^^Λ:)initial — [(ΣΙ^ί)ΐηΐιϊαΙ (S^i)tinalk · (A .2 3 )

W h en Q < 0, th e re is a m in im u m th re s h o ld k in e tic e n e rg y o f th e in c o m in g p a rti­

cles n ee d ed to m a k e th e c ollis io n occu r o r “ g o . ” W e m a y ca lc u la te th e th re s h o ld
k in e tic e n e r g y in th e L - fr a m e (o r la b o r a to r y fr a m e ) fro m th e fa c t th a t th e resu ltin g
p a rticle s are a ll a t re st in th e C -fra m e . T h e exp ression fo r th e th re s h o ld k in e tic
e n e rg y w a s c a lc u la te d in E x a m p le 9.3.
F o r n u clea r re a c tio n s a t r e la t iv e ly lo w en ergies, a ll p a rticle s m a y (in g e n e ra l)
be tr e a te d n o n r e la tiv is tic a lly , so th a t E u = p 2/2m . L e t us co n s id e r th e case in
w h ic h a p r o je c tile o f re st m ass m i an d m o m e n tu m p \ co llid e s w ith a nucleus,
c a lle d th e ta rg e t, o f re st m ass m2 an d a t re s t in th e la b o ra to ry ( p 2 = 0 ), as in
F ig . A - 4 ( a ) . A f t e r th e c o llisio n th e r e s u ltin g p a rticle s m o v e as sh ow n in .F ig . A - 4 ( b ) .

Y Y
P\

I' I
X

Before After

U) (I))

F ig . A -4 . R elation between m om enta relative to the L-fram e before and after a collision.
558 Appendix

C o n s e r v a tio n o f m o m e n tu m g iv e s pi = p[ + P 2 or P 2 = P1 ~ Px- T h e r e fo r e

P '2 = (PX - P i)2 = P? + p '.2 - 2p . p i cos Θ.

U s in g d e fin itio n ( A . 2 2 ) fo r Q, w e h ave

= P t Pi
2 m', 2 m2 2m I
,2 „2
_ Pi PI J_
+I — (p ? + p ',2 - 2 p ip 'i cos Θ)
2m I 22 m
m ,I 2m '2
2m'i

„ I / I . l \ , 2 , 1 / 1 Λ ώ 2 _ Ρ ιΡ
cos Θ.

R e m e m b e r in g th a t E ic = p 2/2m , w e c a n exp ress th e a b o v e re su lt as

Q = EU U + - E kl ( l - - 2 ^ OT'l g t l £ * ‘ COS Θ. ( A . 24)

\ m'2) \ m2/ m'2

T h is resu lt, k n o w n as th e Q-equalion, has m a n y a p p lic a tio n s in n u clea r physics.

W h e n th e c o llisio n is e la stic (Q — 0 ) an d a ll th e p a rticle s are id e n tic a l (m i =
m( — m2 = m 2), th e c o n s e rv a tio n o f e n e r g y g iv e s p [ 2 + p 22 = p\, w h ile fro m th e
c o n s e rv a tio n o f m o m e n tu m , p i = p ! + p 2, w e h a v e p\2 + p 22 + 2p [ · p 2 = p 2.
C o m b in in g th ese results, w e find th a t p( · p2 = 0, o r p[ is p erp e n d ic u la r to p 2.
T h u s , in th e L -fr a m e , th e tw o p a rticle s m o v e a t r ig h t an gles a fte r th e c o llis io n .
T h is m a y b e seen in th e p h o to g ra p h (F ig . A - 5 a ) , w h ic h show s th e collis io n o f tw o

*!·

5 5 ~

(a) (b)
F ig . A -3 . (a ) Collision of tw o equal billiard balls, (b ) Collision of tw o a-particles. In
both cases, one o f the particles was in itially at rest in the L -fram e; their m om enta make
angles o f 90° in the L-fram e after collision [P a rt (a ) courtesy PSSC Phx/sics, Boston:
D .C . H eath],
 Appendix 559

b illia rd balls, o n e in itia lly a t rest. F ig u r e A - 5 ( b ) show s th e c ollis io n o f tw o h eliu m

n u clei in a clou d c h a m b e r; th e in c o m in g h eliu m nucleu s is an α -p a rtic le fro m a
r a d io a c tiv e su b stan ce a n d th e target, h eliu m n ucleu s is fro m th e ga s in th e ch a m b er.
I n b o th cases, th e tw o p a rticle s m o v e a t r ig h t a n g le s a fte r th e collisio n .
A n o th e r in te r e s tin g case is th a t o f a c a p tu re process in w h ic h a p a rtic le o f m ass
W 1 an d m o m e n tu m p j c o llid e s w ith a p a rtic le o f m ass W2 a t rest, an d a sin gle
p a rtic le o f m ass M results. Then p i = pu an d Q — E kM - E i cj. But

E kM = ΡΛ//2Μ = ρ 'ί/2 Μ = E k l( V iJ M ) .
H ence
Q = - E k i ( I — W j /Λ/). ( A . 2 5)

T h e q u a n tit y — Q is th e e x c ita tio n e n e r g y o f th e re su ltin g p a rtic le , such as th e

e x c ita tio n e n e r g y o f a c o m p o u n d nucleu s in a n u clea r re a c tio n . I n m o s t cases
M « w j + W 2 an d th u s

( A . 2 6)

T h e o p p o s ite o f a c a p tu re process, w h ic h is c a lle d an e xp lo sio n , occurs w h en a

p a rtic le e x p lo d e s o r d e c a y s in to tw o o r m o re fra g m e n ts . T h is ta k e s p lace, fo r
ex a m p le, w h e n a g re n a d e e x p lo d e s , w h en a p a rtic le d e c a y s in to s e v e r a l o th e r
p a rticle s, o r w h en a nucleu s u n d erg o es fission. W e shall con sid er th e case in w h ich
th e p a rtic le , o f m ass w , is in itia lly a t re st in th e L -fra m e , w h ic h th en coin cid es
w it h th e C -fra m e . I f th e p a rtic le d iv id e s in to t w o fra g m e n ts o f m asses W 1 an d
w 2, so th a t Q = ( w — W 1 — w 2) c 2, in th e n o n r e la tiv is tic a p p ro x im a tio n w e h a v e

O = P i+ p2 and Q = p 2/ 2 w j + p 2/ 2 w 2.

F r o m th e firs t e q u a tio n w e c on c lu d e th a t p j = — p 2 or pj = p 2. T h u s th e tw o
fra g m e n ts m o v e in o p p o s ite d ire c tio n s w it h m o m e n ta th a t are e q u a l in m a gn itu d e .
T h e seco n d e q u a tio n th e n g iv e s

w h e re μ = W jW 2/ ( w j + w 2) is th e re d u ce d m ass o f th e tw o p a rticles. H ence

Pj = p2 = ( 2 p Q )112 an d th e tw o fra g m e n ts m o v e a p a r t w it h w e ll-d e fin e d m o ­
m e n ta . T h e k in e tic e n e rg ie s o f th e p a rtic le s a re also w e ll d efin ed , a n d are g iv e n b y

I f th e p a rtic le s are tr e a te d r e la t iv is tic a lly , th e re su lt is

560 Appendix

W h e n th e in itia l p a r tic le d iv id e s in to m o re th a n t w o fra g m e n ts , th e ir m o m e n ta

an d e n e rg ie s d o n o t h a v e u n iq u e valu es. T h e c o n s erva tio n e q u a tio n s are

0 = Σ P' ;inci ^ = Σ E t i’
i i

a n d th ese e q u a tio n s can b e satisfied b y s e v e r a l v a lu e s o f p,·. In th e p a rtic u la r case

o f an e x p lo sio n o r d e c a y in to th re e fra g m e n ts , so th a t

O= P l+ P 2 + P3i Q = K kI + K k2 + Klc3,

th e re is a s im p le p ic to r ia l w a y o f re p re s e n tin g th e p ossib le d is trib u tio n o f m o m e n ta

a m o n g th e th re e p a rticles. W e d r a w an e q u ila te ra l tria n g le o f h e ig h t Q (F ig . Λ - G );
th e p e rp e n d ic u la r d ista n ce s fr o m a n y p o in t I' to th e sides o f th e tr ia n g le g iv e th e
v a lu e s o f th e e n e rg y o f th e th re e fra g m e n ts in a g iv e n d e c a y . In a d d itio n , con ser­
v a tio n o f m o m e n tu m re q u ire s th a t th e p o in t P (in th e n o n r e la tiv is tic c ase) be
in sid e th e c irc le o f ra d iu s 3 Q in scrib ed in th e tr ia n g le (in th e r e la t iv is tic case, th e
c u rv e d e p a rts s lig h tly fro m a c irc le ). T h is re p re s e n ta tio n is c a lle d a Dalitz dia­
gram, a n d is w id e ly used to a scerta in w h e th e r a p a rtic u la r m ode o f d ec a y of a
p a r tic le c o rresp on d s to d e c a y in to th re e p a rticles. F o r th e p ro o f o f o u r s ta te m e n t,
n o te th a t pi + p2 > />3 , n ecessarily, an d th a t th e th re e e n e rg ie s can b e exp ressed
as
K kI = P N = I3Q + r cos (φ — § 7r ),

E kO — P M = I1Q + r cos (Φ + § 7r ),

K k3 = P L = '3 Q + r cos φ.

F ig . A - 6 . D a litz diagram for three- F ig . Λ -7 . W a v e pulse,

particle break-up.

III. H roup Y rloritp

L e t us c o n s id e r a h a rm o n ic w a v e w h ich m a y b e d es crib e d b y £ = A sin (kx — ωΐ)
o r b y th e c o m p le x exp ressio n £ = T h is w a v e has an a n g u la r fre q u e n c y
ω a n d w a v e le n g th λ = 2 ττ/k . T h e q u a n tit y v = ω/k. is ca lle d th e phase v e lo c ity .
H o w e v e r , th is is n o t n ec e ss a rily th e v e lo c it y w e o b s e rv e w h e n w e a n a ly z e a w a v e
 Appendix 561

m o tio n . I f w e Iia v e a con tin u o u s h a rm o n ic w a v e (o r as it is so m etim es said , a

w a v e tr a in o f in fin ite le n g th , as in th e exp ression s g iv e n a b o v e ), th e w a v e has a
s in g le w a v e le n g th an d a sin g le fre q u e n c y . B u t a w a v e o f th is n a tu re is n o t a d e ­
q u a te fo r tr a n s m ittin g a sign al, becau se a s ign a l im p lie s s o m e th in g th a t b egin s a t
a c e rta in tim e a n d en d s a t a certa in la te r tim e . T h a t is, th e w a v e m u st h a v e a
sh a p e s im ila r t o t h a t in d ic a ted in F ig . A - 7 . A w a v e w ith such a sh a p e is ca lle d a
pulse. T h e r e fo r e , i f w e m easu re th e v e lo c it y w ith w h ich th e sign al is tra n s m itte d ,
w e a re e s s e n tia lly im p ly in g th e v e lo c it y w ith w h ic h th is pulse tra v e ls .
W e m a y at firs t s a y : W e ll, th is v e lo c it y is ju s t th e phase v e lo c it y v = ω/k ,
since th is is th e v e lo c it y o f p ro p a g a tio n o f th e w a ve s . H o w e v e r , an im p o rta n t
fa c to r e n ters h ere. T h e w a v e o r pulse d e p ic te d in F ig . A - 7 is not h arm on ic, since
its a m p litu d e is n o t c o n s ta n t a lo n g th e Λ’ -axis. T h u s w e m u st m a k e a F o u r ie r
an a lysis o f th e w a v e . W h e n w e d o, w e d is c o v e r th a t it a c tu a lly c o n ta in s s e v e ra l
fre q u e n c ie s an d w a v e le n g th s . O f cou rse, if th e v e lo c it y o f p ro p a g a tio n is in d e ­
p e n d e n t o f th e fre q u e n c y (i.e ., if th e re is n o d is p e rs io n ), th en a ll F o u r ie r c o m ­
p on en ts o f th e p u lse tr a v e l w ith th e s a m e sp eed , an d w e are c o r re c t in s a y in g th a t
th e v e lo c it y o f th e p u lse is th e sam e as th e ph ase v e lo c it y o f th e w a ve s . H o w ever,
in a d is p e r s iv e m e d iu m ea ch F o u r ie r c o m p o n e n t has its o w n v e lo c it y o f p ro p a g a ­
tio n , a n d th e re fo re w e m u st e x a m in e th e s itu a tio n m o re c a re fu lly .
F o r s im p lic ity w e shall c o n s id e r a case in w h ic h th e pulse m a y b e b ro k en d o w n
in to tw o freq u en cies, ω an d ω ', w h ich are a lm o s t e q u a l, so th a t ω ' — ω is v e r y
sm all. W e sh all also assum e th a t th e ir a m p litu d e s a rc th e sam e. T h e n u sin g a
sine w a v e w e h a v e

ξ = A sin (kx — cot) + A sin ( k'x — ω'1)

= A [sin (kx — ω/) + sin (k'x — ω'Ι)]
= 2 A cos ^[(k' — k )x — ( ω ' — ω ) ί ] sin £ [(£ ' -+- k)x — ( ω ' + io)l].

S in ce ω a n d ω ' as w e ll as k an d k' a rc a lm o s t e q u a l, w e m a y re p la c e | (ω ' + ω) by

ω and k (k ' + I;) by k, so th at

ξ = 2 Λ cos i((A ·' — k )x — ( « ' — ω)/] sin (k x — oil). (A . 28)

E q u a tio n (A . 2 8 ) re p res en ts a w a v e m o tio n w h o s e a m p litu d e is m o d u la te d . The

m o d u la tio n is g iv e n b y th e fa c to r

2.4 cos j [ ( U — k)x — (ω' — ω)/].

T h is is in d ic a te d in F ig . A - 8 . T h e m o d u la tin g a m p litu d e its e lf c o rresp on d s to a

w a v e m o tio n p ro p a g a te d w ith a v e lo c it y

ω' — ω do)
( A . 29)
V° k' - k dk ’

w h ic h is c a lle d group velocity. T h is is th e v e lo c it y w it h w h ic h th e a m p litu d e w a v e ,

re p res en ted b y th e d ash ed lin es in F ig . A - 8 , p ro p a g a te s . I f w e re m e m b e r th a t
562 Appendix

ω = kv, E q . ( Λ . 2 9 ) b eco m es

Ve= v+ kW ( Α ·3 0 )

W e can o b ta in th e sam e re su lt i f w e re p res en t th e w a v e in c o m p le x n o ta tio n .

I f th e ph ase v e lo c it y is in d e p e n d e n t o f th e w a v e le n g th , dv/dk = 0 an d ve = v.
T h e r e fo r e in n o n d is p e rs iv e m e d ia th e re is no d iffe r e n c e b e tw e e n phase v e lo c it y
an d g ro u p v e lo c ity , as w e in fe rre d p re v io u s ly . B u t in a d is p e rs iv e m ed iu m th e
g ro u p v e lo c it y m a y b e la r g e r o r s m a lle r th a n th e phase v e lo c ity . W c m a y con ­
clu d e th e n th a t th e m a x im u m o f th e pulse in F ig . A - 7 p ro p a g a te s w it h th e g ro u p
v e lo c it y vg. In q u a n tu m m ech a n ics a p a rtic le lo c a lize d in a re gio n Ax is re p res en ted
b y a w a v e p a c k e t, an d th e p a rtic le v e lo c it y , w h ich is th e e q u iv a le n t o f th e sign al
v e lo c it y , is th e sam e as th e g ro u p v e lo c ity .
A lth o u g h w e h a v e d e r iv e d E q . ( A . 3 0 ) fo r th e case o f o n ly t w o freq u e n cie s, it
also h o ld s tr u e fo r th e case o f a pulse c o n ta in in g freq u e n cie s in th e ra n g e fro m
ω — Δ ω to ω + Δω. W e m u st w a rn th e read er, h o w e v e r, th a t th is m a tte r is r e a lly
m o re c o m p le x th a n o u r p re s e n ta tio n in d ica tes, a n d a th o ro u g h d iscussion o f it is
b e y o n d th e scop e o f th is b ook .

IV . Soimf MrHvfui Intvgraln

In C h a p te r 10 an in te g ra l o f th e fo r m I - $Q e~ax2dx ap p ea red . W e sh a ll n o w
e v a lu a te th is in te g ra l. x, w e use th e s y m b o l y fo r th e
I f in stea d o f th e v a r ia b le
v a r ia b le o f in te g ra tio n , w e m a y w r ite I = J 0 e~a'j2 dy. M u lt ip ly in g th ese tw o
exp ression s, w e h a v e

r ce /*oo

Z2 = / / c~aix2+y2)d xdy.
Jo Jo

T h is d o u b le in te g ra l can b e co n s id e re d as e x te n d e d o v e r th e first q u a d ra n t o f th e
X T - p la n e . T h e result o f th e d o u b le in te g ra l m u st rem a in th e sam e if, in stea d o f
re c ta n g u la r c o o rd in a te s (x, y), w e use p o la r c o o rd in a te s (r, Θ). S in ce x 2 + y~ = r ,
w e h a v e (re p la c in g th e a r e a e le m e n t dx dy by r d f (ΙΘ)
 Appendix 563

T h erefo re

(Λ .3 1 )

a,

f
B y su ccessive d iffe r e n tia tio n w it h re sp e ct to w e o b ta in

oJ

f 4 —α χ 2 j 3 I 7Γ
( A . 33)
Jo Z e “ 8 \ ^ s’

an d so on. O n th e o th e r h an d, b y d ire c t in te g ra tio n w e h a v e

Ja „ — · * - £ (A .3 4 )

and b y d iffe r e n tia tio n o f E q . (A .3 4 ) w ith re s p e c t to a , w e fin d th a t

f x 3e~axl d.t = — ■ ( A . 3 5)

I '. S lirlinf/'s F o rm u la
I n C h a p te rs 10 an d 13 th e e xp ressio n In x ! (w h e r e x is an in te g e r ) is e n c o u n te re d
s e v e ra l tim es . W h en x is very large, an a d e q u a te a p p ro x im a tio n fo r In x\ is

In x\ = x In x — x, ( A . 36)

w h ic h is c a lle d S tirling 's formula. T h is can b e p r o v e d e a s ily in th e fo llo w in g w a y :

In x I = In I + In 2 + In 3 + · · · + In (x — I ) + In x
X

= ^ In x, o n ly i f x is an in te g e r.
I

B u t if x is v e r y la rge, w e can re p la c e th e su m m a tio n b y an in te g ra l w it h o u t g r e a t

e rro r, a n d w r ite

In x I ~ j In x dx.

I n t e g r a t in g b y p a rts w ith u = In x an d du= x, w e fin a lly o b ta in

In x ! = x In x — x + I.

T h e I can b e n e g le c te d w hen c o m p a re d w ith x, a n d E q . ( A . 3 6) resu lts.

564 Appendix

V I. Lugra ngvm
H Tnilvtvrniinvtl NIuItipIivrH
T h is is a m e th o d w h ich s erv e s to fin d th e c ritic a l p oin ts o f a fu n c tio n o f s e v e r a l
v a ria b le s F ( x j, Xi , , x„) w h en th e v a ria b le s a rc n o t in d e p en d en t, b u t are c o n ­
s tra in e d b y c e rta in relation s. S u p pose, fo r ex a m p le, th a t th e c o n s tra in ts are
exp ressed b y Φ ι ( χ ι , x 2, ■ ■ ■ , x«) = 0 and φ2(χ\, X2 x n) = 0. T h e n w e o n ly
have n — 2 in d e p en d en t va ria b le s. T h e c ritic a l p oin ts o f F ( x u x 2, . . . , xn) are
th o se v a lu e s of x t, x 2, . . . , x„ fo r w h ich tlF = 0 fo r sm all ch an ges id th e v a ria b le s .
But
,,, dF , dF , . dF , _ ..
dh = τ— dxi - f τ— dx2 d + τ — dxn = 0 (A .3 7 )
CJJCj Ο.Ι·2

d oes n o t im p ly th a t d F /d x j = 0 b ecau se th e ch an ges dx i, d.c2, . . . , dx„ a re n o t

in d e p en d en t. R a t h e r th e y are re s tric te d b y th e c o n d itio n s

an d
<1φί=Sidx*+Sidx2+■··+SidXn=0 (A-38)
d<t>2 = d^ d x l + dx2 H + ~ d x n= 0. ( A . 3 9)
d.rj ax2 dxn

L e t us n o w m u ltip ly E q s . ( A . 3 8 ) an d ( A . 3 9 ) b y t w o a r b itr a r y q u a n titie s a and β

an d a d d th e m to E q . ( A . 3 7 ). T h e re su lt is

S in ce w e n o w h a v e n + 2 v a ria b le s w ith a an d β a r b itra ry , th is im p lies th a t

i t + ' w + ’ w r 0' ί = Ι ’ 2> · · · ’ η · (Α·40)

T h is set o f n e q u a tio n s a llo w s us to o b ta in X 1, x 2, . . . , x„ fo r a c ritic a l p o in t o f F

as a fu n ctio n o f a an d β. S u b s titu tio n in ^ 1 = 0 an d <f>2 = 0 then g iv e s a an d β,
an d h en ce w e can c o m p u te x lt x 2, . . . , x „ . T h is w a s th e m e th o d used in E x a m p le s
10.1, 13.1, a n d 13.4 fo r o b ta in in g th e m o s t p ro b a b le p a r titio n o f a s y s te m o f p a rti­
cles s u b je c t to th e re q u ire m e n ts (c o n s tra in ts ) o f c o n s e r v a tio n o f p a rticle s an d con ­
s e rv a tio n o f e n e rg y .

V II. Th v U vtvvtion o f I tIirtivIvs

T h e a n a lysis o f processes in v o lv in g fu n d a m e n ta l p a rticle s o r n u c le i re q u ires te c h ­
n iqu es w h ic h n o t o n ly re v e a l th e p assa ge o f a p a rtic le th ro u gh a c e rta in re g io n b u t
in a d d itio n a llo w us to o b ta in in fo rm a tio n a b o u t som e k in e m a tic a l p ro p e rtie s . We
n eed to k n o w th e tim e o f p assage, th e d ire c tio n o f m o tio n , th e v e lo c ity , th e m o m e n ­
tu m o r th e e n e rg y , an d som e in trin s ic p ro p e rtie s such as th e ch a rge, th e mass, o r
th e d ir e c tio n o f th e spin o f th e p a rticle . N o s in g le d e te c tio n m e th o d is c a p a b le o f
 Appendix 565

g iv in g in fo rm a tio n a b o u t a ll th ese q u a n tities . In ge n era l, a c o m b in a tio n o f d e t e c t­

in g d e v ic e s is used fo r o b ta in in g th e in fo rm a tio n re q u ire d in a g iv e n e x p e rim e n t.
T h e d e t e c tin g te c h n iq u e s d ep en d 011 th e e ffe c ts p ro d u ce d b y a c h a rg e d p a rtic le
w h en it m o v e s th ro u gh a sub stan ce. W h e n a c h a rg e d p a rtic le passes th ro u g h
m a tte r, it causes e x c ita tio n an d io n iz a tio n o f th e m o lecu les o f th e m a te ria l. T h is
io n iza tio n is th e p r o p e r ty on w h ich n e a r ly all th e in stru m en ts used fo r th e d e te c ­
tio n o f such p a rticle s are based. S im ila r in stru m en ts can be used fo r u n ch arged
ra d ia tio n s (e .g ., x -ra y s and n eu tro n s ) because, b y m ean s o f collision s, th e y g iv e
e n e r g y to c h a rge d p a rticles, w h ich th en cause io n iza tio n . T h e d iffe r e n t ty p e s o f
in stru m en ts d iffe r w ith re sp e ct t o th e m a te ria l in w h ic h th e io n iza tio n is p ro d u ce d
an d t he w a y it is o b s e rv e d o r m easured.
M a n y in stru m en ts are based o n th e p ro d u c tio n o f io n iza tio n in a gas. It is
n ecessary to s ep a ra te an d c o lle c t th e p o s itiv e an d n e g a tiv e ion s fo r m e d because,
if th e y re m a in e d close to g e th e r, th e y w o u ld re c o m b in e in a v e r y s h o rt tim e an d n o
e le c tric a l e ffe c t w h ich w o u ld re v e a l th e p resen ce o f the p a rtic le cou ld be o b ta in e d .
T h e s e p a ra tio n an d c o lle c tio n o f th e ions re q u ires an e le c tric field , an d d iffe r e n t
in stru m en ts resu lt, d e p e n d in g o n w h e th e r th e fie ld is sm all, la rge, o r in te rm e d ia te
in m a gn itu d e . T h e io n iza tio n m a y also be p ro d u ce d in a liq u id o r in a solid . W h e n
it is p ro d u ce d in a ga s s u p ers a tu ra te d w ith v a p o r , in a su p erh e a ted liq u id , o r in
a p h o to g ra p h ic em u lsion , th e tra c k s o f th e p a rtic le s can b e m a d e v isib le.
W h e n p a rtic le s s trik e certa in liq u id o r s olid m a te ria ls c a lle d phosphors, w h ic h
h a v e th e p r o p e r ty o f lu m in escen ce, p a rt o f th e e n e rg y used in m o le cu la r e x c ita tio n
an d io n iz a tio n is re -e m itte d as v is ib le o r u ltr a v io le t lig h t. S o m e tim e s th is lig h t
can b e o b s e rv e d v is u a lly , o r it m a y h a v e to b e d e te c te d b y m o re s e n s itiv e d evices.
W e sh all co n s id e r s o m e o f th e c o m m o n ly used d e te c tio n m eth o d s, a lth o u g h a
d e ta ile d tr e a tm e n t is b e y o n d th e scop e o f th is b oo k .

A . T h e s c in t illa t io n m e th o d . I t w as fou n d, ab ou t 1!)00, th a t α -p a rtic le s p ro ­

d u ce lu m in escen ce in zin c su lfide, b a riu m p la tin o -c y a n id e , an d d ia m o n d . T h is
lu m in escen ce con sists o f a la rg e n u m b e r o f in d iv id u a l flashes, w h ich can b e seen
th ro u g h a m a g n ify in g glass. C a re fu l e x p e rim e n ts h a v e sh ow n th a t each a -p a r tic le
p rod u ces o n e s c in tilla tio n , so th a t th e n u m b e r o f α -p a rtic le s w h ich fa ll on a d e t e c t­
in g screen is g iv e n d ir e c tly b y th e n u m b er o f s c in tilla tio n s cou n ted . T h e c o u n tin g
can b e d o n e b y m ean s o f a m ic ro sc o p e w ith a m a g n ific a tio n o f a b o u t 30, an d
g o o d p recision can b e o b ta in e d , b u t w it h d iffic u lty . T h is m e th o d is e s p e c ia lly use­
fu l fo r c o u n tin g α -p a rticlc s in th e p resence o f o th e r ra d ia tio n s, b ecau se th e zin c
s u lfid e screen is c o m p a r a t iv e ly in s e n s itiv e to β- an d 7 -rays. T h e m e th o d w a s used
b y R u th e r fo r d in 1910 to a n a ly z e th e s c a tte rin g o f α -p a rtic le s b y n u clei in th in
foils.
T h e use o f s c in tilla tio n c ou n ters has b een v a s t ly im p r o v e d d u e to th e d is c o v e ry
o f n ew lu m in e s ce n t substan ces w h ich are also s e n s itiv e to β- an d 7'-rays, a n d th e
d e v e lo p m e n t o f h ig h ly efficien t p h o to m u ltip lie r tu bes t o d e te c t th e lum inescen ce.
T h e n ew m a te ria ls in clu d e : inorganic sails, p rim a r ily th e a lk a li h alid es, c o n ta in in g
s m all a m o u n ts o f im p u ritie s as a c tiv a to rs fo r lu m in escen ce (f o r e x a m p le , sod iu m
o r p otassiu m io d id e a c tiv a t e d w it h t h a lliu m ); crystalline organic materials, such as
566 Appendix

H-200 V H- I(H)V H-OOOV H- 800 V H-I(K)OV

Paths o f electrons Anode
________ ________ _________ _______H L
Cathode^.

Λ Α / W V *·
Incident ||
light from
phosphor

H -I(H )V / H-300 V +.500 V +7 00 V +900 V

L— Dynode

F ig . A -9 . P hotom u ltip lier tube (schem atic).

n a p h th a len e, an th racen e, an d s tilb c n e ; an d solutions of organic compounds such as

te r p h e n y l d is s o lv e d in x y le n e . T h e p h o to m u ltip lie r tu b e, w h ich rep la ces th e m ic ro ­
sco p e an d o b s e rv e r, c o n v e r ts th e s c in tilla tio n s fro m th e p h o sp h o r in to a m p lifie d
e le c tric a l pulses w h ich can be c o u n te d o r o th e rw is e a n a ly z e d w ith s u ita b le e le c ­
tr o n ic e q u ip m e n t. T h e m o d ern s c in tilla tio n c o u n te r can d e te c t an d re c o rd m a n y
m illio n s o f flashes p er secon d an d can b e used w ith in ten se ra d ia tio n s.
A sch e m a tic d ia g ra m o f a p h o to m u ltip lie r tu b e is s h o w n in F ig . A - 9 . L ig h t
fro m th e lu m in e s ce n t su b stan ce s trik es th e c a th o d e (w h ic h is u su a lly m a d e o f
a n tim o n y an d c esiu m ) an d e je c ts e le c tro n s b y m ean s o f th e p h o to e le c tric e ffe c t.
T h e tu b e has s e v e ra l e lec tro d es , c a lle d dynodes, to w h ich p ro g re s s iv e ly h ig h er
p o te n tia ls a re a p p lied . T h e p h o to e le c tro n s are a c c e le ra te d b y th e e le c tric field
b e tw e e n th e c a th o d e a n d th e first d y n o d e , w h ic h is a t a p o s itiv e p o te n tia l r e la t iv e
to th a t o f th e c a th o d e, an d s trik e th e d y n o d e . T h e a c c e le ra te d e le c tro n s im p a rt
en o u gh e n e rg y to e lec tro n s in th e d y n o d e to e je c t som e o f th em . T h e r e m a y be
as m a n y as ten s e c o n d a ry e le c tro n s fo r each e le c tro n w h ich s trik es th e d y n o d e .
T h e s e s ec o n d a ry e le c tro n s are d ire c te d b y th e e le c tric field to w a rd th e seco n d d y ­
n od e. T h is process is re p e a te d an d th e e lec tro n cu rre n t is a m p lifie d as th e e le c ­
tro n s are a c c e le ra te d fro m d y n o d e to d y n o d e . T h e o u tp u t c u rren t, o r pulse, a t th e
a n o d e m a y b e m o re th a n a m illio n tim e s as g r e a t as th e c u rre n t o r ig in a lly e m itte d

Light reflector

F ig . A -1 0 . S cintillation d etector (schem atic).

 Appendix 567

fro m th e c a th o d e. E a c h p a rtic le in c id e n t on th e p h osp h or p ro d u ces a pulse, and

th e pulses a re fe d to an e le c tro n ic s y stem , in w h ich th e y are cou n ted . E le c tr o n ic
system s h a v e also b een d e v e lo p e d w h ich m easu re th e e n e rg y o f th e in c id e n t p a r­
tic le s; th e re s u ltin g in stru m en t is ca lle d a scintillation spectrometer. A s ch em atic
d ia g ra m o f a s c in tilla tio n d e te c to r is sh ow n in F ig . A - 10.

B. Io n iz a t io n in s t r u m e n t s : io n iz a t io n c h a m b e r, p r o p o r t io n a l c o u n t e r,
a n d G e ig e r - M iille r c o u n te r. T h e p rin c ip le b eh in d each o f th ese d e te c to rs is
th e p ro d u c tio n o f io n iza tio n in a gas an d th e sep a ra tio n an d c o lle c tio n o f th e ions
b y m ean s o f an e le c tric field . T h e d ifferen c es in th e th re e system s can b e e x p la in e d
w ith th e aid o f F ig . A - I I, w h ic h show s a c y lin d ric a l c o n d u c tin g c h a m b er c o n ta in ­
in g a c e n tra l c o n d u c tin g e le c tro d e lo c a te d o n th e axis o f th e c h a m b er an d in su la ted
fro m it. T h e c h a m b e r is filled w ith a gas a t a pressure o f on e a tm o sp h ere o r less.
A v o lt a g e V is m a in ta in e d b e tw e e n th e w a ll an d th e cen tra l e le c tro d e th ro u gh th e
resista n ce R. T h e c e n tr a l e le c tro d e is a t a p o s itiv e p o te n tia l r e la t iv e to th a t o f th e
c h a m b er w a ll.

(b)

F ig . A—11. (a ) Gas-filled counter w ith associated circuit (schem atic), (b ) N u m ber o f

ion pairs collected at the center electrode versus voltage for tw o even ts (curves ( I ) and
( 2 )] with greatly different numbers o f prim ary ion pairs produced.
568 Appendix

S u p p o se th a t io n iz a tio n occu rs in th e gas clue to th e p assage o f a c h a rge d p a r ti­

cle. E a c h io n p a ir consists o f a p o s itiv e io n an d an e le c tro n . F o r a g iv e n in itia l
io n iz a tio n , th e n u m b er o f ion p airs c o lle c te d is a fu n c tio n o f th e a p p lie d v o lt a g e .
In F ig . A - l l ( b ) c u rv es ( I ) and (2 ) o f to t a l ion c o lle c tio n are p lo t te d as fu n c tio n s o f
a p p lie d v o lt a g e fo r tw o d iffe r e n t k in d s o f io n iz in g ra d ia tio n s, such as an a lp h a an d
a b e ta p a rtic le o r tw o b eta p a rtic le s o f d iffe r e n t en ergies. F o r c o n v en ie n ce , th e
lo g a r ith m o f th e n u m b e r o f ion p airs n has been used as th e o rd in a te . I f th e re is
n o v o lt a g e across th e e lec tro d es , th e ions w ill re co m b in e, an d 110 pulse w ill a p p ea r
on th e cou n te r. A s th e v o lt a g e is in creased, s a y t o a fe w v o lts , th e re is c o m p e titio n
b e tw e e n th e loss o f ion p airs b y re c o m b in a tio n a n d th e re m o v a l o f ion s b y c o lle c ­
tio n a t th e e le c tro d e s an d som e e le c tro n s w ill reach th e c e n tr a l e le c tro d e . At a
v o lt a g e F 1 ( o f p erh a p s 10 v o lt s ) th e loss o f io n s b y re c o m b in a tio n is n eg lig ib le ,
an d a ll e le c tro n s p ro d u ced reach th e c e n tr a l e le c tro d e . A s V is in creased, n s ta y s
c o n s ta n t u n til a v o lt a g e F 2 is re a c h ed ; th is v o lt a g e m a y b e s o m e ten s o r h u n d red s
o f v o lts , d e p e n d in g on th e c o n d itio n s o f th e e x p e rim e n t. T h e re g io n Ji b etw e en
F 1 a n d F 2, in w h ich th e n u m b e r o f ion p a irs c o lle c te d is in d e p e n d e n t o f th e a p ­
p lied v o lt a g e an d in w h ic h th e c u rv e is h o rizo n ta l, is c a lle d th e io n iz a tio n cham ber
re g io n .
W h e n th e v o lt a g e is in crea sed a b o v e F 2, n in creases becau se o f a p h en o m en o n
ca lle d gas m u ltip lic a tio n o r gas a m p lific a tio n . T h e e le c tro n s re lea sed in th e p rim a r y
io n iz a tio n a c q u ire en o u gh e n e r g y b e fo re th e y reach th e a n o d e to p ro d u ce a d d itio n a l
io n iz a tio n w h en th e y c o llid e w ith ga s m olecu les, a n d n in creases a lm o s t e x p o n e n ­
tia lly w ith F. E a c h in itia l e le c tro n p ro d u ces a s m a ll “ a v a la n c h e ” o f e le c tro n s ;
m o s t o f th ese s ec o n d a ry e le c tro n s a re lib e ra te d close to th e c e n tra l e lec tro d e.
T h e b e h a v io r o f th e tw o c u rv es a b o v e F 2, c o rre s p o n d in g to d iffe re n t in itia l io n iz a ­
tions, is in te re s tin g . F o r som e ra n g e o f v o lta g e s , up to V 3, each e le c tro n acts
in d e p e n d e n tly an d g iv e s its o w n a v a la n ch e , n o t b e in g a ffe c te d b y th e p resen ce o f
th e o th e r e lec tro n s . H e n c e cu rv es ( I ) an d ( 2 ) c o n tin u e p a ra llel, w ith a c o n s ta n t
r a tio o f n. B e tw e e n F 2 an d I r3, o r re g io n C, th e n u m b er o f ion p airs c o lle c te d is
th en p ro p o rtio n a l to th e in itia l io n iza tio n . T h is is th e re g io n o f p ro p o rtio n a l
c o u n te r o p era tion .
A b o v e F 3, th e g a s -m u ltip lic a tio n e ffe c t con tin u es to in crease v e r y r a p id ly and,
as m o re e le c tro n s p ro d u ce a v a la n ch e s, th e la t te r b e g in to in te ra c t w it h o n e a n o th e r;
th e p o s itiv e -io n sp a ce c h a rge o f o n e a v a la n c h e in h ib its th e d e v e lo p m e n t o f th e
n e x t a v a la n c h e . T h e d isc h a rge w ith m o re in itia l e le c tro n s (c u r v e 2 ) is a ffe c te d
b e fo r e th e o n e w ith fe w e r in itia l e le c tro n s (c u r v e I ) an d increases less r a p id ly th an
th e la t te r ; c u rv e s ( I ) a n d ( 2 ) a p p ro a c h each o th e r an d e v e n tu a lly m e e t a t an
a p p lie d v o lt a g e Vr4. T h e re g io n F> b e tw e e n F 3 an d F 4 is th e re g io n o f lim ite d
p ro p o rtio n a lity . A b o v e F 4 th e c h a rge c o lle c te d b eco m es in d e p e n d e n t o f th e io n iz a ­
tio n in itia tin g it, an d c u rv e s ( I ) an d (2 ) b eco m e id e n tic a l. T h e gas m u ltip lic a tio n
in creases th e to ta l n u m b er o f io n s to a v a lu e th a t is lim ite d b y th e c h a ra c te ris tic s
o f th e c h a m b e r an d th e e x te r n a l c irc u it. T h e re g io n E a b o v e F 4 is th e re g io n o f
G e ig e r -M iille r coun ter op era tion . I t ends a t a v o lt a g e F 3, w h e re th e d isch arge
ten d s to p ro p a g a te its e lf in d e fin ite ly ; F 5 m a rk s th e end o f th e usefu l v o lt a g e scale,
th e re gio n F a b o v e b e in g th a t o f c o n tin u o u s discharge. A s a re su lt o f th e b e h a v io r
 A ppendix 569

o f th e ion s o f th e gas in th e e le c tric fie ld o f th e c o u n te r, th re e d e te c tio n in stru m en ts

h a v e b een d e v e lo p e d .

1. T h e io n iz a tio n cham ber, w h ich o p e ra te s a t v o lta g e s in th e re g io n B, is ch a ra c ­

te riz e d b y c o m p le te c o lle c tio n o f a ll th e e le c tro n s in itia lly lib e ra te d b y th e p assage
o f th e p a rtic le w ith o u t gas a m p lific a tio n . S u b je c t to c e rta in con d itio n s, it w ill g iv e
a p u lse p ro p o rtio n a l in m a g n itu d e to th e n u m b e r o f th ese electro n s. I t is used to
m easu re th e in te n s ity o f an io n iz in g ra d ia tio n b y m ea su rin g th e ra te o f io n iza tio n .

2. T h e p ro p o rtio n a l counter, w h ich o p e ra te s in th e v o lt a g e regio n C , is ch a ra c ­

te riz e d b y a ga s m u ltip lic a tio n in d e p en d en t o f th e n u m b er o f in itia l electro n s.
H e n c e , a lth o u g h gas m u ltip lic a tio n is u tilize d , th e pulse is a lw a y s p ro p o r tio n a l to
th e in itia l io n iza tio n . T h e use o f th is c o u n te r p erm its b oth th e c o u n tin g o f s in g le
e v e n ts an d th e d e te rm in a tio n o f th e e n e rg y o f p a rticle s w h ich d o n o t p ro d u ce
en ou gh io n s to y ie ld a d e te c ta b le pulse in re g io n B. T h e p ro p o rtio n a l cou n ter,
th e re fo re , o ffe rs a d v a n ta g e s fo r p u ls e -ty p e m ea su rem en ts o f b e ta ra d ia tio n , an
a p p lic a tio n fo r w h ich io n iz a tio n ch a m b ers are n o t s u ffic ie n tly s en sitive.

3. T h e G e iy e r -M iille r counter, also k n o w n as th e G eiyer o r G - M coun ter, w h ich

o p e ra te s in th e v o lt a g e re gio n E , is c h a ra c te rized b y th e sp read o f th e d isc h a rge
th ro u g h o u t th e e n tire le n g th o f th e cou n te r, re s u ltin g in a pu lse size in d e p en d en t
o f th e in itia l io n iza tio n . I t is e s p e c ia lly usefu l fo r th e c o u n tin g o f lig h tly io n iz in g
p a rticle s such as /3-particles o r 7 -rays. T h e G -M c o u n te r u s u a lly con sists o f a
fin e w ir e (e .g ., tu n g s te n ) m o u n ted a lo n g th e axis o f a tu b e w h ich c o n ta in s a gas at
a pressure o f a b o u t 2 to 10 c m o f m e rc u ry. T h e c o u n te r m a y be a tu b e m a d e o f a
m e ta l such as c o p p er, o r a m e ta l c y lin d e r s u p p o rted in sid e a glass tu b e ; a m ix tu re
o f 9 0 % a rg o n an d 1 0 % e th y l a lc o h o l is s u ita b le fo r th e gas. A p o te n tia l d iffe re n c e
(w h ic h m a y b e b e tw e e n 800 a n d 1200 V ) is a p p lie d to m a k e th e tu b e n e g a tiv e
w ith re s p e c t to th e w ire.
In th e G e ig e r - M iille r regio n a con tin u ou s d isch arge is p ro d u ce d b y th e release
o f s ec o n d a ry e lec tro n s fro m th e w a lls o f th e tu b e d ue to side e ffec ts tr ig g e re d b y
th e in itia l a v a la n c h e o f ions. T h e s e s ec o n d a ry e lec tro n s resu lt because, w h en a
p o s itiv e a rg o n ion, fo r in stan ce, is n eu tra lize d on th e m e ta llic su rface o f th e c a th ­
o de, a c o n s id e ra b le am ou n t o f e n e rg y is re lea sed w h ich m a y be used to e x p e l an
e le c tro n fro m th e c a th o d e su rface. T h e s e e lec tro n s , in m o v in g to w a r d th e cen tra l
e le c tro d e , p ro d u ce n ew io n iza tio n s, thus p e rp e tu a tin g th e d isch arge. T o p rep a re
th e c o u n te r fo r a n e w e v e n t it is n ecessary to s to p o r “ qu en ch ” th e d isch arge. T h is
q u en c h in g m a y b e a ccom p lish ed b y e le c tro n ic a lly lo w e rin g th e v o lt a g e V a fte r
each cou n t. H o w e v e r , th e q u en c h in g is u su a lly d on e in th e gas its e lf. I f , fo r e x ­
a m p le, th e gas is a rg o n w ith 10 % e t h y l a lc o h o l, th en because o f c h a rge e xch an ges
in collis io n s o f a rg o n ion s w ith a lc o h o l m olecu les, th e p o s itiv e io n s re a c h in g th e
c a th o d e a re a lc o h o l ions, an d th e y d o n o t, in ge n era l, release e lec tro n s fro m th e
c a th o d e s u rfa c e; th e e n e rg y is used in stea d to b rea k th e a lco h ol m o lecu le an d th e
d isc h a rge q u ic k ly s to p s a fte r th e in itia l a v a la n c h e reach es th e e lectro d es. S ec o n d ­
a r y e le c tro n s are also re lea se d b y p h o to n s p ro d u ce d in th e a v a la n ch e . T h e a lc o h o l
m o le cu les ab sorb th e p h o ton s w ith o u t re le a s in g electro n s.
570 Appendix

In th e e le c tric a l in stru m en ts discussed, th e ions, e ith e r m u ltip lie d in n u m b e r or

n o t, are c o lle c te d and p ro d u ce a v o lt a g e pulse w h ich m a y b e as s m a ll as 10 pV . An
e le c tro n ic pulse a m p lifie r a ccep ts th ese sm all v o lta g e s an d a m p lifies th e m to a le v e l
u s u a lly in th e ra n g e o f 5 to ό0 V . T h e a m p lifie d v o lt a g e pulses m u st th en b e
c o u n te d in som e w a y so th a t th e ir ra te can b e m easured. T h e n u m b e r o f pulses
in d ic a te d on th e c o u n te r g iv e s th e n u m b e r o f p a rtic le s th a t h a v e e n te re d th e sp a ce
b e tw e e n th e elec tro d es . O th e r e le c tro n ic d e v ic e s are also a v a ila b le fo r m easu rin g
th e m a g n itu d e o f th e pulse w h ic h g iv e s th e e n e rg y o f th e in c id e n t p a rtic le . Thus
on e o fte n w a n ts n o t o n ly to re c o rd th e o ccu rren ce o f a pulse, but also to s o rt pulses
a c c o r d in g to th e ir size ( b y m ea n s o f an e le c tro n ic d is c rim in a to r c ir c u it) o r to s ort
th e m a c c o r d in g to th e tim e in te r v a ls d u rin g w h ich th e y a r r iv e (b y m ean s o f an
e le c tro n ic tim in g c irc u it). T h e d e te c to r th en fo rm s p a rt o f a c irc u it w ith a p p ro ­
p ria te e le c tro n ic in stru m en ta tio n .

C. N e u t ro n d e te c tio n . M o s t p rocesses in v o lv e d in s to p p in g n eu tro n s in m a t­

t e r m a y b e used fo r d e te c tin g n eu tron s, since c h a rge d p a rticle s are set in to m o tio n ,
e ith e r as a p rim a r y e ffe c t o r as a s e c o n d a ry e ffe c t a fte r th e em ission o f a g a m m a
ra y. T h e p rocesses u tilize d in n e u tro n d e te c tio n a re:

(1 ) n eu tro n -in d u ced n u clea r re a c tio n s y ie ld in g c h a rged p a rtic le re a c tio n p ro d ­

ucts (p ro to n s , a lp h a p a rticles, e tc .),
( 2) in d u ce d fission in c e rta in h e a v y elem en ts,
(3 ) e la s tic collisio n s b e tw e e n n eu tro n s an d nuclei, n o ta b ly h y d ro g e n n u clei,
w h ich are th e re b y set in to m o tio n ,
(4 ) c a p tu re o f n eu tron s b y c e rta in s ta b le isotopes, w h ich are th e re b y c o n v e r te d
in to ra d io is o to p e s e m itt in g β- an d 7 -ra y s (a c tiv a t io n m e th o d ).

T h e classical e x a m p le o f n e u tro n d e te c tio n is th e b oron c o u n te r fo r s lo w n eu tron s.

T h is is a gas c o u n te r in w h ich th e in sid e w a ll is lin ed w ith b oron o r th e c o u n te r
is fille d w ith B F 3 gas, p r e fe r a b ly e n rich e d in 10B . T h e re sp o n sib le re a c tio n is
10B ( n , a ) 7 L i. T h e alp h a p a rtic le an d th e 7L i re c o il nucleu s b oth h a v e s h o rt ran ges,
so th a t in m o s t o f th e e v e n ts th e y c o m e to rest in th e ga s w ith a ll th e relea sed
e n e rg y c o n v e r te d in to io n iza tio n an d a to m ic e x c ita tio n s. T h e c o u n te r is o p e r­
a te d in th e p r o p o r t io n a lity re g io n , a n d it is thus re a s o n a b ly e a s y to d is c rim in a te
b e tw e e n th e n eu tro n -in d u ced e v e n ts an d th o se d u e to g a m m a -r a y o r c o s m ic -ra y
b a c k gro u n d . O th e r e x a m p les o f re a c tio n s th a t h a v e b een used fo r slo w -n eu tro n
d e te c to rs are 6 L i ( n , t ) 4H e , l 4N ( n , p ) 14C , an d I 13C d (n ,7 ) 114C d .
N u c le a r re a c tio n s h a v e also been u tilize d in fast- n eu tro n d e te c to rs ; h o w e v e r,
th e e ffic ie n c y is n o t so h igh as in th e b o ro n c ou n ters fo r s lo w n eu tron s, since 110
fa s t-n eu tro n cross section com es a n y w h e re close to th e m a g n itu d e o f th e 10B
cross s ectio n fo r s low n eu tron s. S in ce th e B F 3 c o u n te r is such an e ffic ie n t and
s im p le c o u n te r fo r s lo w n eu tron s, o n e n a tu ra l w a y o f m a k in g a d e t e c to r fo r fa s t
n eu tro n s is to su rrou n d a B F 3 c o u n te r w it h p a ra ffin in w h ic h th e fa s t n eu tro n s slow
d o w n b y e la s tic collisio n s so th a t t h e y can d iffu s e in to th e c o u n te r as th e rm a l
n eu tro n s. T h e c o m p le te fa s t-n eu tro n c o u n te r can b e m a d e in se n sitive to slow
n eu tro n s b y ca d m iu m sh ield in g.
 Appendix 571

F ig . A -1 2 . L igh t w a ve fron t in C’ erenkov radiation.

D . T h e C erenU ov c o u n te r. The v e lo c it y of lig h t in a tra n sp a ren t solid or

liq u id is g iv e n b y v = c/n, w h e re n is th e in d e x o f re fra c tio n . I f a c h a rg e d p a rtic le
m o v in g th ro u g h th is m ed iu m has a v e lo c it y g re a te r th a n v (th a t is, g r e a te r th a n
th e v e lo c it y o f ligh t in th e m e d iu m ), lig h t is e m itt e d b y th e a to m s th a t are m o m e n ­
ta r ily e le c tr ic a lly p o la rize d b y th e ch a rged p a rtic le p assin g n ea rb y. T h e process is
o n e in w h ich th e p e rtu rb a tio n o f (h e e le c tric field on th e a to m p ro d u ces a tra n sie n t
d ip o le m o m e n t, w h ic h th en causes em ission o f e le c tro m a g n e tic w a v e s . T h e reason
w h y such lig h t is e m itt e d o n ly w h en th e v e lo c it y exceed s v = c/n is th a t o n ly in
this case can lig h t fro m all a to m s a lo n g th e tra c k b e coherent,. F ig u r e Λ - 1 2 show s
h o w a w a v e fr o n t ca'n b e c o n s tru cted fro m e le m e n ta ry w a v e s e m itt e d fro m v a rio u s
p oin ts a lo n g th e p a th o f th e p a rticle . F o r a g iv e n v e lo c it y Vt o f th e p a rtic le , th e
lig h t is e m itt e d in a cone, w it h th e a n g le a g iv e n b y sin a - v/v, — c/n vt . A
s iza b le fr a c tio n o f th e C e r e n k o v ra d ia tio n is g iv e n o ff in th e v is ib le p a rt o f th e
sp ectru m , w h ich also corresp on d s a p p r o x im a te ly t o th e region o f h igh es t sensi­
t i v i t y o f p h o to m u ltip lie r tubes. V a r io u s t y p e s o f C e r e n k o v d e te c to rs h a v e b een
b u ilt, in w h ich o n ly th e lig h t e m itt e d in a p a rtic u la r d ire c tio n is reco rd ed . The
d e te c to r th en is a v e lo c ity - s e n s itiv e d e v ic e . O b v io u s ly it can b e used o n ly fo r p ar­
tic le s w ith va > c/n.

E . T h e c lo u d c h a m b e r. O n e o f th e m ost im p o r ta n t in stru m en ts fo r b asic re­

search on ra d ia tio n is th e c lou d ch a m b er. T h is in stru m en t, first used in 1912, is
based o n th e d is c o v e r y b y C . T . R . W ils o n th a t ions act as n u clei fo r th e con ­
d en satio n o f s u p ers a tu ra te d w a te r v a p o r. I n a clou d ch a m b er, th e gas, s a tu ra ted
w ith v a p o r , is m a d e to ex p a n d b y th e q u ic k m o tio n o f a p iston . T h e e xp an sio n is
a d ia b a tic a n d lo w e rs th e te m p era tu re . T h e c o o lin g is m o re th an su ffic ien t to o v e r ­
c o m e th e e ffe c t o f th e in crease in v o lu m e , an d th e a ir b ecom es s u p ers a tu ra te d w ith
572 Appendix

w a te r v a p o r . I f an io n iz in g r a y e n te rs th e ch a m b er, th e io n s fo r m e d a c t as c on ­
d en s a tio n p o in ts fo r th e v a p o r, a n d th e p a th o f th e r a y ap p ea rs as a th in tr a c k o f
fo g . I n m o s t e xp an sio n ch am b ers, th e g a s - v a p o r m ix tu re is a ir w it h w a te r, or
a rg o n w ith e t h y l alco h ol, a t a tm o s p h e ric pressure.
A s im p lifie d d ia g ra m w h ich in d ic a tes th e p rin c ip le o f th e c lou d c h a m b e r is
sh o w n in F ig . A - 1 3 . A c y lin d e r C is closed a t o n e e n d b y a glass w in d o w W and
a t th e o th e r en d b y a m e ta l p iston . A s m a ll a m o u n t o f w a te r in th e c h a m b er
keeps th e a ir s a tu ra ted . W h e n th e p iston is p u lle d d o w n , th e a ir b ec o m es su p er­
s a tu ra ted as d escrib ed a b o v e an d, in th e p resen ce o f io n iz in g ra d ia tio n , fo g tra ck s
are fo rm ed . T h e tra c k s can be illu m in a te d b y lig h t fro m th e side a n d v ie w e d o r
p h o to g ra p h e d th ro u g h th e w in d o w . T h e io n s can then b e re m o v e d b y m ean s o f
an e le c tric field b e tw e e n th e p iston a n d th e m e ta l rin g. T h e p iston is re tu rn e d to
its o rig in a l p o s itio n an d th e c h a m b er is r e a d y fo r a n o th e r b u rst o f ra d ia tio n .

If
LiRht source

F ig . A -1 3 . W ilson cloud chamber

(schem atic).

T h e W ils o n clou d c h a m b er m a k es it p ossible to s tu d y th e in te ra c tio n s th a t ta k e

p la c e b e tw e e n c h a rge d p a rticle s an d in d iv id u a l a to m s by p h o to g ra p h in g th e
a c tu a l p ath s o f io n iz in g ra d ia tio n s, w h ic h m a y th en b e a n a ly z e d a t leisu re. M any
m o d ific a tio n s o f th e o rig in a l clou d c h a m b er h a v e been m a d e. F o r e x a m p le , in
o rd e r to o b ta in la rg e n u m b ers o f p h o to g ra p h s, a rra n g e m e n ts h a v e been m a d e so
th a t th e exp a n s io n can b e re p e a te d a u to m a tic a lly an d p h o to g ra p h s ta k e n c o n ­
tin u o u sly . I f tw o s te reo s co p ic p ictu re s are ta k e n s im u lta n eo u sly, th e p a th o f th e
p a rtic le in space can b e re co n stru cted .
W h e n a clou d c h a m b er is p la ced b e tw e e n th e p o le p ieces o f an e le c tro m a g n e t it
is p os s ib le to d istin g u is h b e tw e e n p o s itiv e ly an d n e g a tiv e ly c h a rg e d p articles.
F r o m th e c u rv a tu re o f th e p a th o f a p a rtic le in th e m a g n e tic field , th e sign o f th e
c h a rg e an d th e m a g n itu d e o f th e m o m e n tu m o f th e p a rtic le can b e d eterm in e d .
D iffe r e n t p a rticle s p ro d u ce d iffe r e n t ty p e s o f tracks. T h u s h e a v y , s lo w p a rticle s
such as α -p a rt id e s p ro d u ce b ro ad , d e n s e ly p a c k e d tra c k s w it h o ccasio n al sharp,
s m a ll-a n g le bends, e s p e c ia lly n ea r th e en d o f th e tra c k , d u e to a su d den d e v ia tio n
re s u ltin g fro m a collisio n . S lo w e le c tro n s p ro d u ce n a rro w , b ea d ed , to rtu o u s tracks,
since th e y u n d ergo m a n y sca tte rin g s , w h ile fa s t p a rticles, b o th lig h t an d h e a v y ,
p ro d u ce n a rro w , b ea d e d tracks.

F . T h e b u b b le c h a m b e r. F o r h ig h -e n e rg y p a rticles, o n e d is a d v a n ta g e o f th e
c lou d c h a m b er is th a t th e d e n s ity o f th e ga s is n o t g r e a t en o u gh to cause an a p ­
p re c ia b le n u m b e r o f in te ra c tio n s to ta k e p la c e in th e ch a m b er. M o r e im p o rta n t
p erh a ps is th a t th e clou d c h a m b er has a v e r y lo n g r e c o v e r y tim e ( o f th e o rd e r o f
 Appendix 573

ten s o f s eco n d s) a fte r each exp an sio n . I n e le m e n ta ry -p a rtic le research , th e re fo re ,

th e clou d c h a m b e r has been a ll b u t rep la ced b y th e b u b b le ch a m b er, w h ich is, on e
m ig h t say, an in v e rs e clou d ch a m b er. Λ b u b b le c h a m b er c o n ta in s a liq u id at a
p ressure an d te m p e r a tu re such th a t it is ju s t b e lo w its b o ilin g p oin t. I f th e pressure
is s u d d e n ly d ec re a s ed th e liciuid b eco m es su p erh e a ted an d b u b b les s ta r t to d e v e lo p ,
p r e fe r e n t ia lly fo r m in g a rou n d ions. In th e h y d ro g e n b u b b le ch a m b er, s u p er­
h ea te d liciuid h y d ro g e n ( ~ 20 ° K ) is th e m ed iu m th ro u g h w h ich th e p a rticle s pass.
T h e ions le ft in th e p a th o f a c h a rg e d p a rtic le b ec o m e e v a p o r a tio n n u clei fo r th e
liq u id h y d ro g e n , an d th e tra il can b e seen an d p h o to g ra p h e d as a ch a in o f bubbles.
W h e n p a rtic le s w h ic h in te ra c t s tr o n g ly w ith p ro to n s pass th ro u gh th e b u b b le
ch a m b er, re a c tio n s ta k e place, an d th e tra ils o f th e in c o m in g p a rticle , as w e ll as
th e re a c tio n p ro d u cts, can b e stu d ied . I f th e b u b b le c h a m b e r is p la ced in a m a g ­
n e tic field an d p h o to g ra p h s a re ta k e n , th e c h a rge an d th e m o m e n tu m o f th e
v a rio u s p a rtic le s can be m easu red in th e p h o tog rap h s.

G . T h e s p a rk c h a m b e r. O n e o f th e n ew es t in v e n tio n s in th e a rea o f h igh -

e n e rg y d e te c to rs is th e spa rk ch a m b er, w h ich con sists o f a n u m b e r o f m e ta llic
p la te s in su la ted fro m each o th e r an d w ith a u n ifo rm n e o n -fille d g a p o f th e o r d e r o f
a fe w m illim e te rs b etw e en th em . E v e r y o th e r p la te is gro u n d ed , an d th e in te r-
le a fin g p la te s are g iv e n a short v o lt a g e pulse (0 .5 ps) o f such a m a g n itu d e th a t
s parks w ill occu r a t places a t w h ich th e gas is io n ize d . T h e tr a il o f ion s le ft b y a
p e n e tr a tin g p a rtic le w ill tr ig g e r such sp a rk s; a p h o to g ra p h o f th e sp a rk s b e tw e e n
a ll th e p la te s g iv e s an o u tlin e o f th e p ath o f th e p a rticle .

I I . / 'h o lo g ra p h ic e m u ls io n s . A n io n iz in g p a rtic le tr a v e lin g th ro u gh th e e m u l­

sion o f a p h o to g ra p h ic p la te le a v e s a tr a c k c o n ta in in g a n u m b e r o f sen s itize d s ilv e r
b ro m id e gra in s. S p e c ia l p h o to g ra p h ic em u lsion s, ca lle d n u clear em u lsion s, h a v e
been d e v e lo p e d . T h e y arc d istin g u is h e d fro m o p tic a l em u lsion s b y th e ir h igh s il­
v e r b ro m id e c o n te n t (w h ic h m a y b e as m u ch as fo u r tim es as g re a t as in p h o to ­
g ra p h ic p la te s ), b y g ra in size, an d b y th e th ick n ess o f th e em u lsion , h ik e th e
c lou d c h a m b er, th e p h o to g ra p h ic p la te, w h e n it has b een d e v e lo p e d , re co rd s th e
p a th o f th e p a rticle , an d a v a r ie t y o f in fo r m a tio n can be o b ta in e d fr o m th e s tu d y
o f th e track s. C o u n tin g th e in d iv id u a l p ath s g iv e s a m easu re o f th e n u m b e r o f
p a rticle s e n te r in g th e p late, a n d d e ta ile d s tu d y o f th e tra ck s y ie ld s in fo rm a tio n
a b o u t th e mass, ch a rge, an d e n e r g y o f th e p a rticle s. T h e p h o to g ra p h ic em u lsion
o ffe rs a d v a n ta g e s o v e r th e clou d c h a m b er in th a t th e em u lsion is solid , so that· th e
tra c k s are sh ort, an d its s e n s itiv ity is p e rm a n e n t ra th e r th an re s tric te d to in fr e ­
q u e n tly re p e a te d s h o rt in te rv a ls . O n th e o th e r hand, to re co rd specific e ve n ts , th e
d iffe r e n t c h a m b ers can b e c o n tro lle d b y m ean s o f coin c id e n ce circu its, a process
w h ic h is n ot p o s s ib le w ith p h o to g ra p h ic em ulsions.
 TABLES

A N SW E RS TO
O D D -N U M B E R E D PRO BLEM S

IN D E X
 Table .4-3 Units and Sym bols
Q u a n tity Sym bol N a m e o f u n it R e la tio n to fu n d a m e n ta l u n ite
M KSC M KSA

Length I, s meter m
Mass m kilogram kg
T im e t second S

V elocity V m 3- I
Acceleration a m s -2
Angular velocity ω S- I
Angular frequency ω S- I
Frequency V hertz (H z ) 8" I
M om entum V m kg s _1
Force F newton ( N ) m kg s -2
Angular momentum L m 2 kg s _1
T orque τ m 2 kg s -2
W ork W joule (J) m 2 kg s -2
Pow er P w a tt (W ) m 2 kg s -3
E nergy Pkt Fpt Ut F joule (J) m 2 kg s -2
Tem perature T 0K m 2 kg s 2/particle
Coefficient of diffusion D m 2 5- i
Coefficient of thermal
conductivity K m kg s~ 3 O R - I

Coefficient o f viscosity
Y o u n g’s modulus
Bulk modulus
Shear modulus
M om en t o f inertia
G ravitation al field
G ravitation al potential
V m _ I kg s -1
Y m -1 kg s -2
K m _1 kg s ~ 2
G m _ ! kg s -2
I m 2 kg
S m s -2
m2 3- 2

Charge < 1 ,Q coulomb C A s

Electric current I ampere s -‘ C A
Electric field ε m kg s -2 C -1 m kgs" 3 A - 1
E lectric potential V v o lt (V ) m 2 kg s -2 C -1 m 2 kg s - 3 A -
Current density j m -2 s -1 C m -2 A
Electric resistance R ohm (Ω) m 2 kg s _1 C -2 m 2 kg s -3 A '
Inductance L henry (H ) m 2 kg C - 2 m 2 kg s “ 2 A "
E lectric p erm ittivity «O m -3 k g -1 s2 C 2 m _3 kg - 1 s A
Polarization <P m -2 C m ~2 s A
D ielectric displacement 2D m -2 C m -2 s A
M agnetic field CS tesla ( T ) kg s -1 C -1 kg s -2 A -1
M agnetic perm eability MO m .kg C -2 m kg s -2 A -2
M agnetization 311 m -1 s -1 C m _1 A
M agn etizin g field 3C m _1 s _1 C m -1 A
M agnetic flux Φ® weber (W b ) m 2 kg s _1 C -1 m 2 kg s - 2 A '
E lectric dipole moment V m C m sA
E lectric quadrupole moment Q m2 C m2 s A
M agnetic dipole moment M m2 s- 1 C m2 A
M agnetic quadrupole moment Q m 3 s -1 C m3 A
C apacity C farad (F ) m -2 k g -1 S2 C 2 m “ 2 k g-> s4 /
 Tables

NATU RAL T R IG O N O M E T R IC F U N C T IO N S

An gle A n gle

D e­ Ra­ C o­ Tan­ D e­ R a­ C o­ Tan­

gree dian Sine sine gent gree dian Sine sine gent

0° .000 0.000 1.000 0.000

1° .017 .018 1.000 .018 46° 0.803 0.719 0.695 1.036
2° .035 .035 0.999 .035 47° .820 .731 .682 1.072
3° .052 .052 .999 .052 48° .838 .743 .669 1.111
4° .070 .070 .998 .070 49° .855 .755 .656 1.150
5° .087 .087 .996 .088 50° .873 .766 .643 1.192
6° .105 .105 .995 .105 51° .890 .777 .629 1.235
7° .122 .122 .993 .123 52° .908 .788 .616 1.280
8° .140 .139 .990 .141 53° .925 .799 .602 1.327
9° .157 .156 .988 .158 54° .942 .809 .588 1.376
10° .175 .174 .985 .176 55° .960 .819 .574 1.428
11 ° .192 .191 .982 .194 56° .977 .829 .559 1.483
12 ° .209 .208 .978 .213 57° .995 .839 .545 1.540
13° .227 .225 .974 .231 58° 1.012 .848 .530 1.600
14° .244 .242 .970 .249 59° 1.030 .857 .515 1.664
15° .262 .259 .966 .268 60° 1.047 .S66 .500 1.732
1 G° .279 .276 .961 .287 61° 1.065 .875 .485 1.804
17° .297 .292 .956 .306 62° 1.082 .883 .470 1.881
18° .314 .309 .951 .325 63° 1.100 .891 .454 1.963
19° .332 .326 .946 .344 64° 1.117 .899 .438 2.050
20 ° .349 .342 .940 .364 65° 1.134 .906 .423 2.145
21 ° .367 .358 .934 .384 66 ° 1.152 .914 .407 2.246
22 ° .384 .375 .927 .404 67° 1.169 .921 .391 2.356
23° .401 .391 .921 .425 68 ° 1.187 .927 .375 2.475
24° .419 .407 .914 .445 69° 1.204 .934 .358 2.605
25° .436 .423 .906 .466 70° 1.222 .940 .342 2.747
26° .454 .438 .899 .488 71° 1.239 .946 .326 2.904
27° .471 .454 .891 .510 72° 1.257 .951 .309 3.078
28° .489 .470 .883 .532 73° 1.274 .956 .292 3.271
29° .506 .485 .875 .554 74° 1.292 .961 .276 3.4S7
30° .524 .500 .866 .577 75° 1.309 .966 .259 3.732
31° .541 .515 .857 .601 76° 1.326 .970 .242 4.011
32° .559 .530 .848 .625 77° 1.344 .974 .225 4.331
33° .576 .545 .839 .649 78° 1.361 .978 .208 4.705
34° .593 .559 .829 .675 79° 1.379 .982 .191 5.145
35° .611 .574 .819 .700 80° 1.396 .985 .174 5.671
36° .628 .588 .809 .727 81° 1.414 .988 .156 6.314
37° .646 .602 .799 .754 82° 1.431 .990 .139 7.115
38° .663 .616 .788 .781 83° 1.449 .993 .122 8.144
39° .681 .629 .777 .810 84° 1.466 .995 .105 9.514
40° .698 .643 .766 .839 85° 1.484 .996 .087 11.43
41° .716 .658 .755 .869 86 ° 1.501 .998 .070 14.30
42° .733 .669 .743 .900 87° 1.518 .999 .052 19.08
43° .751 .682 .731 .933 88 ° 1.536 .999 .035 28.64
44° .768 .695 .719 .966 89° 1.553 1.000 .018 57.29
45° .785 .707 .707 1.000 90° 1.571 1.000 .000 OO
578 Tables

COMMON L O G A R IT H M S

N 0 I 2 3 4 5 6 7 8 9

0 0000 3010 4771 6021 6990 7782 8451 9031 9542

I (KKK) 0414 0792 1139 1461 1761 2041 2304 2553 2788
') 3010 3222 3424 3617 3802 3979 4150 4314 4472 4624
3 4771 4914 5051 5185 5315 5441 5563 5682 5798 5911
4 6021 6128 6232 6335 6435 6532 6628 6721 6812 6902
5 6990 7076 7160 7243 7324 7404 7482 7559 7634 7709
6 7782 7853 7924 7993 8062 8129 8195 8261 8325 8388
7 8451 8513 8573 8633 8692 8751 8808 8865 8921 8976
8 9031 9085 9138 9191 9243 9294 9345 9395 9145 9494
9 9542 9590 9638 9685 9731 9777 9823 9868 9912 9956
10 O(KK) 0043 0086 0128 0170 0212 0253 0294 0334 0374
11 0414 0453 0492 0531 0569 0607 0645 0682 0719 0755
12 0792 0828 0864 0899 0934 0969 1004 1038 1072 1106
13 1139 1173 1206 1239 1271 1303 1335 1367 1399 1430
14 1461 1492 1523 1553 1584 1614 1644 1673 1703 1732
15 1761 1790 1818 1847 1875 1903 1931 1959 1987 2014
16 2041 2068 2095 2122 2148 2175 2201 2227 2253 2279
17 2304 2330 2355 2380 2405 2430 2455 2480 2504 2529
18 2553 2577 2601 2625 2648 2672 2695 2718 2742 2765
19 2788 2810 2833 2856 2878 2900 2923 2945 2967 2989
20 3010 3032 3054 3075 3096 3118 3139 3160 3181 3201
21 3222 3243 3263 3284 3304 3324 3345 3365 3385 3404
22 3424 3444 3464 3483 3502 3522 3541 3560 3579 3598
23 3617 3636 3655 3674 3692 3711 3729 3747 3766 3784
24 3802 3820 3838 3856 3874 3892 3909 3927 3945 3962
25 3979 3997 4014 4031 4048 4065 4082 4099 4116 4133
26 4150 4166 4183 4200 4216 4232 4249 4265 4281 4298

27 4314 4330 4346 4362 4378 4393 4409 4425 4440 4456
28 4472 4487 4502 4518 4533 4548 4564 4579 4594 4609
29 4624 4639 4654 4669 4683 4698 4713 4728 4742 4757
30 4771 4786 4800 4814 4829 4843 4857 4871 4886 4900
31 4914 4928 4942 4955 4909 4983 4997 5011 5024 5038
32 5051 5065 .5079 5092 5105 5119 5132 5145 5159 5172
33 5185 5198 5211 5224 5237 5250 5263 5276 5289 5302

34 5315 5328 5340 5353 5366 5378 5391 5403 5416 5428
35 5441 5453 5465 5478 5490 5502 5514 5527 5539 5551
36 5563 5575 5587 5599 5611 5623 5635 5647 5658 5670
37 5682 5694 5705 5717 5729 5740 5752 5763 5775 5786
38 5798 5809 5821 5832 5843 5855 5866 5877 5888 5899
39 5911 5922 5933 5944 5955 5966 5977 5988 5999 6010
40 6021 6031 (>042 (3053 6064 6075 6085 6096 6107 6117
41 6128 6138 6149 6160 6170 6180 6191 6201 6212 6222
42 6232 6243 6253 6263 6274 6284 6294 6304 6314 6325
43 0335 6345 6355 6365 6375 6385 6395 6405 6415 6425
44 6435 6444 6454 6464 6474 6484 6493 6503 6513 6522
45 6532 6542 6551 6561 6571 6580 6590 6599 6609 6618
46 6628 6637 6646 6656 6665 6675 6684 6693 6702 6712

47 6721 6730 6739 6749 6758 6767 6776 6785 6794 6803
48 6812 6821 6830 (>839 6848 6857 6866 (>875 6S84 6893
49 6902 6911 6920 6928 6937 6946 6955 6964 6972 6981
50 6990 6998 7007 7016 7024 7033 7042 7050 7059 7067

N 0 I 2 3 4 5 6 7 8 9
 Tables 579

COMMON L O G A R I T H M S ( continued)

N 0 I 2 3 4 5 6 7 8 9

50 6990 6998 7007 7016 7024 7033 7042 7050 7059 7067
51 7076 7084 7093 7101 7110 7118 7126 7135 7143 7152
52 7160 7168 7177 7185 7193 7202 72 ro 7218 7226 7235
53 7243 7251 7259 7267 7275 7284 7292 7300 7308 7316
54 7324 7332 7340 7348 7356 7364 7372 7380 7388 7396
55 7404 7412 7419 7427 7435 7443 7451 7459 7466 7474
56 7482 7490 7497 7505 7513 7520 7528 7536 7543 7551

57 7559 7566 7574 7582 7589 7597 7604 7612 7619 7627
58 7634 7642 7649 7657 7664 7672 7679 7686 7694 7701
59 7709 7716 7723 7731 7738 7745 7752 7760 7767 7774
60 7782 7789 7796 7803 7810 7818 7825 7832 7839 7846
61 7853 7860 7868 7875 7882 7889 7896 7903 7910 7917
62 7924 7931 7938 7945 7952 7959 7966 7973 7980 7987
63 7993 8000 S007 8014 8021 8028 8035 8041 8048 8055
64 8062 8069 8075 8082 8089 8096 8102 8109 8116 8122
65 8129 8136 8142 8149 8156 8162 8169 8176 8182 8189
66 8195 8202 8209 8215 8222 8228 8235 8241 824S 8254

67 8261 8267 8274 8280 8287 8293 8299 8306 8312 8319
68 8325 8331 8338 8344 8351 8357 8363 8370 8376 8382
69 8388 8395 8401 8407 8414 8420 8426 8432 8439 8445
70 8451 8457 8463 8470 8476 8482 8488 8494 8500 8506
71 8513 8519 8525 8531 8537 8543 8549 S555 8561 8567
72 8573 8579 8585 8591 8597 8603 8609 8615 8621 8627
73 8633 8639 8645 8651 8657 8663 8669 8675 8681 8686
74 8692 8698 8704 8710 8716 8722 8727 8733 8739 8745
75 8751 8756 8762 8768 8774 8779 8785 8791 8797 8802
76 8808 8814 8820 8825 8831 8837 8842 8848 8854 8859

77 8865 8871 8876 8882 8887 8893 8899 8904 8910 8915
78 8921 8927 8932 8938 8943 8949 8954 8960 8965 8971
79 8976 8982 8987 8993 8998 9004 9009 9015 9020 9025
80 9031 9036 9042 9047 9053 9058 9063 9069 9074 9079
81 9085 9090 9096 9101 9106 9112 9117 9122 9128 9133
82 9138 9143 9119 9154 9159 9165 9170 9175 9180 9186
83 9191 9196 9201 9206 9212 9217 9222 9227 9232 9238

84 9243 9248 9253 9258 9263 9269 9274 9279 9284 9289
85 9294 9299 9304 9309 9315 9320 9325 9330 9335 9340
86 9345 9350 9355 9360 9365 9370 9375 9380 93S5 9390

87 9395 9400 9405 9410 9415 9420 9425 9430 9435 9440
88 9445 9450 9455 9460 9465 9469 9474 9479 9484 9489
89 9494 9499 9504 9509 95t3 9518 9523 9528 9533 9538
90 9542 9547 9552 9557 9562 9566 9571 9576 9581 9586
91 9590 9595 9600 9605 9609 9614 9619 9624 9628 9633
92 9638 9643 9647 9652 9657 9661 9666 9671 9675 9680
93 9685 8689 9694 9699 9703 9708 9713 9717 9722 9727

94 9731 9736 9741 9745 9750 9754 9759 9763 9768 9773
95 9777 9782 9786 9791 9795 9800 9805 9809 9814 9818
96 9823 9827 9832 9836 9841 9845 9850 9854 9S59 9863

97 9868 9872 9877 9881 9886 9890 9894 9899 9903 9908
OS 9912 9917 9921 9926 9930 9934 9939 9943 9948 9952
99 9956 9961 9965 9969 9974 9978 9983 9987 9991 9996
100 0000 0004 0009 0013 0017 0022 0026 0030 0035 0039

N 0 I 2 3 4 5 6 7 8 9
Tables

E X P O N E N T IA L F U N C T IO N S

X ez e z X ez e~z

0 .0 0 1.0000 I .0000 2 .5 12.182 0.0821

0 .05 1.0513 0.9512 2 .6 13.464 0.0743
0 .1 0 I.1 0 5 2 0.9048 2 .7 14.880 0.0672
0 .15 1.1618 0.8607 2 .8 16.445 0.0608
0 .2 0 1.2214 0.8187 2 .9 18.174 0.0550

0 .25 I.2840 0.7788 3 .0 20.086 0.0498

0 .30 1.3499 0.7408 3.1 22.198 0.0450
0 .35 1.4191 0.7047 3 .2 24.533 0.0408
0 .40 1.4918 0.6703 3 .3 27.113 0.0369
0 .45 I.5683 0.6376 3 .4 29.964 0.0334

0 .50 I.6487 0.6065 3 .5 33.115 0.0302

0 .55 I.7333 0.5769 3 .6 36.598 0.0273
OGO 1.8221 0.5488 3 .7 40.447 0.0247
0 .65 1.9155 0.5220 3 .8 44.701 0.0224
0 .70 2.0138 0.4966 3 .9 49.402 0.0202
0 .75 2.1170 0.4724 4 .0 54.598 0.0183
0 .80 2.2255 0.4493 4.1 60.340 0.0166
0 .85 2.3396 0.4274 4 .2 66.686 0.0150
0 .90 2.4596 0 4066 4 .3 73.700 0.0136
0 .95 2.5857 0.3867 4 .4 81.451 0.0123

1.0 2.7183 0.3679 4 .5 90.017 0.0 111

1.1 3.0042 0.3329 4 .6 99.484 0.0101
1.2 3.3201 0.3012 4 .7 109.95 0.0091
1 .3 3.6693 0.2725 4 .8 121.51 0.0082
1.4 4.0552 0.2466 4 .9 134.29 0.0074

1.5 4.4817 0.2231 5 148.41 0.0067

1.6 4.9530 0.2019 6 403.43 0.0025
1.7 5.4739 0.1827 7 1096.6 0.0009
1.8 6.0496 0.1653 8 2981.0 0.0003
1.9 6.6859 0.1496 9 8103.1 0.0001
2 .0 7.3891 0.1353 10 22026 0.00005
2 .1 8.1662 0.1225
2 .2 9.0250 0.1108
2 .3 9.9742 0.1003
2 .4 11.023 0.0907
 LIST OF TABLES

T able 2-1. E n ergy levels and degeneracies in a cubical box 69

T able 2-2. W a v e functions of a harmonic oscillator 72
T able 2-3. Vibrational energy levels for axial m otion o f N atom in N I I 3 molecule
relative to the ground state 87
T a b l e 2-4. Quantum operators 99
T a b l e 3-1. R yd b e rg’ s constant 112
T a b l e 3-2. E nergy corrections when nuclear motion is considered 115
T a b l e 3-3. Designation of angular mom entum states and essential degeneracy
for m otion under central forces 118
T able 3-4. Angu lar functions corresponding to L 2 and L t 123
T able 3-5. Angu lar functions corresponding to L 2 and L 2 123
T able 3-6. R adial wave function o f hydrogcnliko atom s 125
T able 3-7. Designation of electronic states 139
T able 4-1. E lectronic configuration o f atom s 162
T able 4-2. T erm s o f equivalen t electrons 166
T able 4-3. Possible mi and m, values for the n p 2 configuration 170
T able 5-1. E lectronic configuration of homonuclear diatom ic molecules 196
T able 5-2. Dissociation energy, bond lengths, and electric dipole moments of
some diatom ic molecules 199
T able 5-3. R otation al and vibration al constants o f some diatom ic molecules 213
T able 6-1. Ferm i energy 249
T able 6-2. E ffective mass 257
T able 6-3. E nergy gaps 265
T able 7-1. P ro p e rtie s o fs o m e n u c lid e s 291
T able 7-2. N u m b er o f stable and v e r y lon g-lived nuclides 315
T able 8-1. T h e u ra n iu m s e rie s 331
'! ' a b l e 8-2. Q-values for emission o f different nuclear particles from 232U 340
T able 8-3. Fission ab ility o f h ea vy nuclei w ith therm al neutrons 358
T able 8-4. Threshold energies for photofission 358
T able 8-5. Properties o f some fissionable materials for therm al neutrons 360
T able 9-1. Fundam ental particles 378
T able 9-2. Particle decay modes 387
T able 9-3. Isotopic spin, strangeness, and hypercharge o f mesons and Iraryons 400
T able 10-1. Values of e r f ( i ) 459
T able 12-1. V an der W aals constants 503
581
582 Lisl o f Tables

T able 12-2. Characteristic tem peratures for rotation and vibration of d iatom ic
molecules 508
T able 12-3. R atios of the heat capacities for some gases 514
T able 13-1. Ferm i energy and Ferm i tem perature o f several metals 524
T able 13-2. Values of the work function and the therm ionic constant obtained
experim entally from E q. (13.11) 527
T able 13-3. D eb ye temperatures o f some solids 538
 ANSW ERS TO O D D -N U M B ER ED PROBLEM S

CHAPTER I

1.1 (b) IOeV = 1.6 X IO" 19 J, 5 X IO4 eV = 8.01 X I O -13J, I MeV = 1.6 X 10“ 13 J
(c) 0.004c, 0.299c, 0.814c
1.3 1.78 X IO3 J
1.7 (a) i X IO" 9 T (b) 1.33 X 10“ ° W m “ 2 (c) 4.22 X 10~ 13 J m " 3
(d) 1.4 X IO-23 m “ 2 kg s - 1 ; (e) 167 W
1.9 e (v ) = (Snhv3/c3) e~h' /kT; e (v ) = 8irhTv 2/cz
1.11 4100°K; 0.214 J m “ 3
1.13 (a) 1.70 X IO10 electrons m " 2 s " 1 (b) 3.0 X IO -9 W m " 2; (c) 1.76 X IO" 19 J
1.15 (a) 4.555 X IOl i Hz (b) 1.88 eV (c) 4.1274 X I O -15J s C - 1
1.17 (a) 1.024 X IO-10 m (b) 4.71 X IO-17 J, 44.3° with respect to the incident
direction
1.19 166.8 keV = 2.67 X IO" 14 J, 7.43 X IO" 12 m
1.23 (a) 5.03 X IO21 photons m “ 3 (b) 2080 photons m -3
1.25 (a) 1.24 X 10“ 9 m (b) 1.24 X IO" 0 m (c) 1.24 X 10~4 m
1.27 (a) 4.892 eV (b) 6.7064 eV, 4.8922 eV, 3.9614 eV, 2.2723 eV, 2.1465 eV
1.29 2.65 X IO15 Hz, 1.13 X 10~7 m
1.31 3.1 X IO" 11 m
1.33 7.5 X IO-3 eV in excess of the binding energy
1.37 127
1.39 1.05 X ΙΟ” 4 m, 2.39 X IO" 3 m, 8.77 X IO" 3 m
1.41 (a) 8 (b) 40 (c) 100
1.43 7.9S cm, 8.06 cm
1.47 5°47'
1.49 (a) for the proton: 3.9 m, for an electron: 7.3 X IO3 m
(b) with unlimited precision for both cases
1.53 1.03 X IO9 Hz or 4.26 X 10“ 6 eV; 5.15 X IO14 Hz or 2.13 M cV
1.55 (a) A E k = - 4 E k/A

C H A PTE R 2

2.3 Energy difference between levels (a) increases (b) decreases

2.5 3.8 X IO3 M cV ; Egrav - 6.31 X 10~ 17 eV, Ecoul = 1.44 X IO4 MeV
583
584 Answers to odd-numbered problems

2.13 (a ) {ma2/2irti2) dE (b ) (a2p/2wh2) dp

2.15 (a ) 8.27 X IO - ' 3 c V (b ) 2.48 X IO - ' 2 c V (c ) 1.34 X 10“ 3 eV
2.21 22.7 M e V
2.23 (a ) B = [ — Λ ( a 2 + k2) sinh aa\/R, C = Atk2 - ik o )e -aa/R ,
D = — Atk2 + ika) Caa/ R, A ' = — 2A tika)e~xka/ R,
where R = ( a 2 — k2) sinh act —2 iak cosh aa
( b ) B = - X A t j d 2I k 2 - I ) sin k 'a / R ' , C = - A ( k ' / k + 1 ) β - “ ' « / Λ '
D = - A t k '/ k - I )eik'-/R ', Λ ' = — 2 Λ tk '/k )e -ika/ R ',
where R ' = itk'2/ k 2 + I ) sin k'a — 2 (k'/k) cos k'a
2.25 E < E 0-. Φλ = Ae~ikx + Bcxtz, φ3 = Ce0'* + De~a'x, φ2 = Eea" 1 + Fe~a" z,
φ I = G e-ikl;
E 0 < E < E 0: φ\ and ψ;\ as above, Φ2 = Eexk" x + Fe~xi" z, φ\ as ab ove;
E > E 0: φ\ as above, φ:ι = Ceik'x -j-De~xi x, Φ2 = EJeik" 1 - f Fe~ik" x, φ i as above
2.27 E < E 0: φ i = Aeikx + Be~ikx, φ2 = C e- " ' + Deax, Φά = Eeikx + Fe~ikx,
φχ = C,e-ax+ IIeax, φ$ = Ieikx;
E > Ε 0:φ ι,φ 3 , and φ$ as above, Φ2 = Ceik x + De—'i z , φι = Gexkx + Ι Ι 0- Λ ζ .
2.29 (a ) { - Ι ι 2/2ηι)ά2φ/άχ2 - Ζιφ = Εφ (b ) N o
2.31 (d ) - E 0 + h(aE0/2 m y 12
2.39 F o r d/dx: (a ) Yes, ik (b ) Y es, a (c ) N o . F o r d2/d x 2: (a ) Y es, —k2 (b ) Y es, a 2
(c ) Yes, — k 2
2.41 F o r n = 0 :0 , Α/2πιω, 0, ^mtua; for η = 1 :0 , h/6moi, 0, 3Jmhoi
2.43 L1 = —ihtyd/dz — zd/d y); Lp = — ih(z d/dx — xd /dz); L, = — ih(x d/dy — y d/dx)
2.45 y/h/2ma>, 0/— i \ / 0
2.47 Δη = ±1 , ±3 , ±5 , . . .

CHAPTER 3
3.1 ω = 4.134 X IO 1V n 3 S - 1 J F p = — 4.36 X I O - 1V n 2 J j F l = 2.18 X 1 0 ~ I 8/n2 J
3.3 (a ) 8.22 X 10° orbits (b ) 1.95 X IO 4 orbits
3.5 Δ λ ,,.η = 1.78 Λ, Δ λ „ _ τ = 2.38 A
3.9 (a ) 6.58 X 10 15/n 3 H z (b ) 6.58 X 1015(n — %)/[n(n — I )]2 H z
3.17 L1 = —ih \ — sin φ d/dO — (c o t 0 cos φ) d/d<f>];
Lp = — ϊ!ι[οοίφ d/dO — (c o t β sin φ) β/<Ίφ]
3.29 2αο
3.33 Δ/ίρ = § Α ; A Ed = §Α, J sA l AEt = §Α, ^ A 1J 5A,
where A = 2 |F„| Ζ 2α 2/η
3.35 Ycs (Δ λ = 8.2 X ΙΟ -11 m)
3.37 2.41 X IO -21 N ; 0.042 mm 3.39 2.8 X IO 9 H z

CHAPTER 4
4.1 — 5 7 .8 eV , — 55.9 eV , — 55.2 e V ; relative to the H e + ion ( — 54.4 e V ) these are
- 3 . 4 eV , — 1 .5 eV , - 0 . 8 eV
 Answers Io odd-numbered problems 585

Φ ι.Χ + ( 1 ) ψι.Χ+(2) ii.X + (3 )

4.3 ψ ι*22η = -Z L lA i.X _(l) iAi,X_(2) iAi.X_(3)

Vo
^ 2sX+(l) ^2.X+(2) ψ2»Χ+(3)

* ,X +(1) φ,Χ+(2) * ,X +(3)

4.5 ^ ap2 = 4 = ψρ(+ 1)Χ + (1) * p( + l) X + (2) ψρ(+1)Χ + (3)

Vb
^ p(O )X-(I) "Ap(O )X-(2) AP(0)X -(3)

4.7 See Table 4-1 for values.

4.11 (a) 2S (b) 2P1 2D 1 4S ( c ) 2S, 2D 1 2P1 4P (d) 2P (e) 2P, 2D 1 2F 1 2G 1 2H 1
4S, 4P1 4F 14G (f) 1S1 1P1 1D 1 1F 1 1G 13S 1 3P, 3D 1 3F1 3G
4.15 0, 0, 0; i 0, 0, I, I; I, I, 2; I, 3, 4; 2, 2, I; 0, 2, 2; f , 3, §
4.19 Calcium: aluminum: £
4.21 6439 A and (6439 ± 0.26) A
4.25 8.58 A
4.27 Lithium: 2s, —5.315 eV ; 2p, —3.54 eV ; 3s, — 2.01 eV
Sodium: 3s, —5.120 e V ;3 p , —3.028 eV ; 4s, — 1.967 eV (3d at - 1 . 5 2 eV)
4.29 Aluminum: 1.9 keV, 115eV ; oxygen, 1.1 keV, 46 eV
4.31 Aluminum: 8.40 A, 1470eV; potassium: 3.59 A, 3452eV ; iron: 1.74 A, 7121 eV;
nickel: 1.55 A, 7965 eV ; zinc: 1.34 A, 9221 eV ; molybdenum: 0.664 A, 18,700 eV;
silver, 0.525 A, 23,600 eV
4.33 (b) 8.3 keV, 1.495 A

CH APTER 5

5.1 (a) — 16.25 eV (b) 10.95 eV (c) 15.43 eV

5.3 61.06 kcal mole-1
5.7 (b) (σκIs) 2(auI s)2(σβ2s) 2(au2s)2(σκ2ρ) 2(ττυ2ρ)4 (πβ2ρ) 4(σ„2ρ) 2(aK3s) 2
(au3s)2(σκ3ρ)2(ττυ3ρ)4(πβ3 ρ )2; 3 Σ Κ“
5.9 (a) L i+H - (b) H +I "
5.11 5.45 eV
5.13 8.37 eV ; 6.45 eV
5.23 5.06 X IO" 30 m C ; 0.33
5.25 17.7 A
5.27 2.83 A
5.29 For H 35Cl: (a) 21.5015 cm " 1 (b) 2.6658 X IO" 3 eV, 7.9974 X IO" 3 eV
(c) 6.450 X IO11 Hz (4.651 X IO" 4 m ), 12.900 X IOn Hz (2.326 X IO" 4 m)
(d) 21.50 cm " 1
5.31 (a) E rot = Vd + D + i m2]h2/ 2 Ii, (b) E rot = Vd + I) - * m * »* / 2 h
5.35 1.906 X IO3 N m " 1
5.37 5.162 X IO2 N m - 1JO-ISei eV
586 Answers to odd-numbered problems

C H A P T E R 6

6.1 3.686 eV
6.3 6.371 e V m olecule - 1
6.5 3 X IO 12H z
6.9 6.934 X IO 5 kg s- 2 ; 4.885 X IO 15 s - 1 , 6.026 X IO 15 s -1
6.11 4.560 X IO28 atom s m - 3 ; 8.498 X IO 2.8 atoms m - 3 ; 1.660 X IO 29 atom s m - 3
6.13 3.151 e V ; 4.445 eV
6.17 m* = h / 2a, and S2XiZdl2 = 2 F a J h 2, where i stands for x, y, z,respectively.
6.21 mr/2a (b ) h2/(2βα2 cos ka)
(a )
6.23 4.811 X IO -12 m
6.25 A p p roxim ately I atom in IOe^ Aj '
6.27 3.63 X 10- 14 p; 1.39 X 10® m s - 1 ; 1.98 X IO 7 m - 1 ; 5.05 X IO - 8 m
6.29 10ο 6.33 1.057 X IO -1 0 m 3 C - 1 ; 62.1° 6.35 1.65 microns

C H A P T E R ?

7.5 3.62 X IO -1 5 m ; 6.90 X IO -1 5 m ; 8.28 X IO -1 5 m

7.7 28S i 1 29S i1 30Si
7.13 0.85 M e V ; 0.76 M e V 1 yes
7.15 7 L i: 39.24 M e V 1 5.61 M e V nucleon- 1 ; 16O : 127.62 M e V 1 7.98 M e V nucleon- 1 ;
57 F e : 499.90 M e V 1 8.77 M e V nucleon- 1 ; 176L u : 1417.97 M e V 1 8.06 M e V nucleon -1
7.17 13(27A1); 28(®4N i ) ; 3 6 (82K r ); 5 2 (125T e ) ; 7 2 (180H f)
7.19 5.062 X IO - 3 amu
7.21 1.0078217 amu, 2.014100 amu, 15.99492 amu

7.27 2.16 X IO -1 3 m
7.29 3.62 X IO 4 particles s -1
7.31 2.80 X IO -1 5 m
7.33 0.150 b
7.35 (a ) 2H : (ls i/ 2) P(ls i/ 2) n; H : ( l s i /2) p(ls ? /2) „ ; 3 H e: (Is fz 2) p( I s 1Za)n;

4H e : (ls ? /2) P(ls i/ 2)n; C : ( l s i /2l p 3 /2, P( l s 1/2 l p 3 /2) „ ;

13C : (ls ? /2 l p 3/2) P(ls i/ 2 lP 3 /2 lp i/ 2)n (b ) 0 or I ; £ ; £; 0; 0; %
7.37 A = 50, 222 k eV ; A = 100, 7 4 k e V ; A = 150, 38.2 keV

C H A P T E R 8

8.1 (a ) 7.86 X IO - 8 S-1 (b ) 5.27 X 10 11 s - 1 ; 112 y r (d ) 1.32 X IO 4 s -1

8.9 28 m g 8 .1 3 m «
8.17 Qs+ = 0.64 M e V ; Qr = 0.565 M e V ; Qec = 1.66 M e V
8.19 18.63 keV
8 23 (a ) 24N a (b ) i ° P (c ) ? iP (d ) 7 (e ) f H ( f ) 1JSln (g ) %Cu (h ) 7
8.27 12C (P ) 7 ) I 3 N ; 12C (d, 7 ) l 4N , 12C (d , p ) 13C, 12C (d , n ) 13N , 12C (d , a ) 10B ; 12C (a , 7 ) 160
 Answers Io odd-numbered problems 587

8.29 (a ) 27.98245 am u (b ) 23.98676 amu (c ) 27.98192 am u (d ) 24.98586 amu

8.31 (a ) 1.535 M e V (b ) 2.34 M e V
8.33 A straigh t line
8.35 (a ) 1.74 X IO 14 atom s (b ) 22 b
8.37 1.806 X IO - 6 8.39 2.77 cm
8.41 188 M e V 8.43 1 .2 X IO " 8 k g s " 1 ; 2 .6 y r
8.45 232T h : 4.95 M e V ; 233T h : 6.11 M e V ; 233U : 5.85 M e V ; 234U : 5.26 M e V ;
239Pu : 6.45 M e V ; 240P u : 5.41 M e V
8.47 7.28 M e V ; 2.92 X IO 23 W
8.49 1.28 X IO u y r

C H A P TER 9

9.1 (a ) 3.7 (b ) 5.26 X IO 3

9.3 (a ) 2.53 keV (b ) 2.85 X IO " 13 m (c ) 1IrA g
9.5 L e s t mass: 502 M e V ; E k-. 6S0 M eV
9.7 7480 M e V
9.9 F o r Fig. 9-10: 1840 M e V ; for F ig. 9-11: 1810 M e V
9.15 (a ) 0.511 M e V (b ) forw ard : 1.44 M e V l b ackw ard: 0.58 M e V
9.17 (a ) 8.3 G e V (b ) 68 G e V
9.19 143.8 M e V
9.21 (a ) 3 , = I, 3P = J, 3Λ = 0 , 3 * = £ (b ) 3 , - I , 3Ρ = J 1 3Λ = 0 , 3 , = 0 ,
cannot occur due to nonconservation o f 3, 3., and §.
9.23 (a ) P + + P + P + + A0+ Iv 4
3, : i i i 0 JL
2
3: i i J 0 I

S: 0 0 0 - I I

3., 3, and S are conserved.

9.25 3., 3, and S are conserved; 2710 M e V
9.33 £ remains invariant; (B goes to — ® .

C H A P TER 10
10.1 0.206; 1.014
10.3 3480 0K
10.5 (b ) U = — μ Β® Α ' tanh (μ Β(R f k T ) (c ) as T —* 0, Z —» 2 and .1/ —> —μ%(Rn/kT;
as T —» » , Z —* oo and Al —> — μΒη
10.9 U = — /ub®j7[(,7 + 2 ) coth ( j + J )x — J coth Jx]
10.11 ( E i / E 2) ll2e - (Bi - Ei )lkT (a ) 6.3 X 10“ 9 (b ) 0.395 (c ) 2.54
10.13 (a ) 4.8 X IO 3 m s " 1, 4.4 X IO 3 m s- 1 , 3.9 X IO 3 m s " 1 (b ) 2.25 X IO 3 m s " 1,
3.9 X IO 3 m s ' 1, 7.12 X IO 3 m s " 1, 2.25 X IO 4 m s _1
10.15 (a ) 1.11 X IO 3 m s ” 1 (b ) 5.16 X IO 3 m s " 1 (c ) 2.16 X IO 3 m s ’ 1
088 Answers Io odd-numbered problems

10.17 (a ) 0.166 (b ) 0.163

10.23 (a ) 4 2 % (b ) 8 % (c ) 43.8% (d ) 6.2%
10.27 (a ) 0 % (b )3 5 % (c ) 9 3%
10.31 (b ) λ = k/(2 m k T )'12 = 1.81 X IO - ' 0 m

CHAPTER I l
11.1 (a ) 8.1 X IO3 J (b ) 1.62 X IO4 J
11.3 (a ) 60 J (b ) 70 J; liberated (c ) Qai = SO J 1 Qot = IO J

11.7 (a ) Q = a (T 2 - T 1) + b (T l - T il ) + c (~ - -

(b ) C p .vo = O + b(T 2 + T i) — c /T IT 2
(c ) AS = a In ( T 2/ T , ) + 2b (T 2 - T 1) - CZT1T 2
(d ) 24.0 X IO 3 J 0 K - 1 m o le - ’ , 23.6 X IO 3 J 0 K " 1 m o le -*

11.15 S int = —kN ^ ta n h (t/k T ) — In 2 cosh (e / A T )l;

C v int = kN In 2 cosh (t/k T )

11.19 (b ) 224.5 Ca l0K - '
11.21 (a ) T = ( 0 II/0 S )p, K = (OHfOp)s (b ) p = -(O F fO V )r , S = - (O F f d T )v
(c ) V = (0G/0p)r , S
(OGfdT)p = —
11.23 A ll are extensive except for p, T, and (OIIfOS)p, which are intensive.
11.27 AS = L f T = 5.28 cal 0K - ' m o l e - '; I I = L = 1440 cal m o le- 1 ;
A U = A U — p A V = 1440.05 cal m o le -1
11.33 3.49 X IO 3 J; 3.49 X IO3 J; 0; 0; 11.6 J 0K - '

C H A P T E R 12
12.1 W = uR T In ( K 2/ K i) — n 2(K 7 '6 — a) — ^ j+ " I 1427.3 J

12.5 (a ) Kr = I /P ( b) * r = K 2( K - n6) 2/ {n R T K 3 - 2N2a (K - n&)2}

12.7 (a ) p f T - ' ^ T = C (b ) T V y - ' = C
12.13 (b ) T i K l - ' = T 2V l - ', T 2 = 212 0K 1 T 3 = 88.5 0K (c ) 3.25 X IO4 J
12 15 (b ) 1Κΐ2 = 16-90 X IO 5 J; IK 23 = 0; IK3I = — 13.02 X IO 5 J; IKr = 3.88 X IO 5 J 1
A S 12 = 5.39 X IO3 J 0K - ' , A S 23 = - 5 . 3 9 X IO 3 J 0K " ' ; A S 31 = 0; A S t = 0
12.17 T = Br, Z = 0: 36.9% , 1 = 1: 43.2% ; T = 2 Θ „ 1 = 0: 30.2% , I= 1: 55.3%
12 19 1.2 X 10° molecules o f H 2l 2.65 X IO2' molecules o f C l 2

C H A P T E R 13
20 IcT 13.15 e ( v) = (Sttv 2A 3 )A-T 13.27 2.09 X 10~ 7
 IN D E X

Absolute temi>craturc, 444, 482 Balm er, J. (1825-1898), 117

Absorption edge, 178 Balm cr formula, 115
Absorption spectrum, 22 Band, conduction, 246
A ccep tor, 266 valence, 246
Acoustical branch, 241 Barn, 290
A ctin iu m series, 329 B arrier penetration, 80
A c tiv ity , 332 B aryon, 378
A d iab atic com pressibility, 516 B aryon quantum number, 399
A d iab atic dem agnetization, 486 Benzene (C o H o ) molecule, 211, 279
A d iab atic transform ation, 474, 484 Bergm ann scries, 173
A lp h a decay, 335 B eryllium , energy levels of, 175
A lp h a particle, 329 B eta particle, 329
A m m onia ( N i l s ) molecule, 202 B eta decay, 340
w a ve functions for inversion motion of, 85 Bethe cycle, 365
energy levels, table of, 87 B inding energy, 76
Anderson, C. (1905- ), 380 nuclear, 293
Angu lar m omentum , conservation of, 403 B lackbody radiation, 8 , 531
nuclear, 288 B loch ’s theorem , 251, 259
quantization of, 118 Bohr, N . (1885-1962), 22, 117
spin, 135 B ohr form ula, 22
total, 135, 164 Bohr magneton, 133
Angu lar w ave functions, 123 Bohr radius, 113
Annihilation, electron pair, 381 Boltzm ann, L. (1844-1906), 11 , 436,
proton-antiproton, 381 482
An tiparticle, 379 Boltzm ann constant, 444
A n tiproton , 385 Bond, covalent, 198
A ntincutrino, 341 ionic, 198
A nti-Stokes line, 221 x - and σ-, 205
Associated production, 402 Born, M . (1882- ), 239
Atm osphere, 465 Bose, S. (1894- ), 528
A to m ic mass, 286 Bose-Einstein distribution law, 529
A to m ic mass unit, 286 Boson, 519, 528
A to m ic number, 109, 283 massless, 378
A u ger effect, 178 B o y le ’s law, 465
589
590 Index

Uoyle tem perature, 515 C o n du ctivity, 269

B rack ett series, 116 intrinsic, 265
Bragg condition, 36 Conductor, 261
Bragg scattering, 253 Configuration, 158
Bremsstrahlung, 6 Conjugated molecule, 208
Brillouin zones, 253 Conservation, o f angular m omentum , 103
Bubble chamber, 572 o f baryons, 399
Bulk modulus, 278, 516 o f charge, 404
isotherm al, 488 o f energy, 404
o f isotopic spin, 399
Calcium , energy levels of, 174 o f leptons, 398
Calorie, 466 of momentum, 403
Carbon cycle, 365 o f p arity, 406
Carbon, en ergy levels of, 168 o f particles, 63
Carbon dioxide (C 0 > ) molecule, 219 o f strangeness, 402
C a rn ot cycle, 485, 496 C on tact potential difference, 527
C a rn ot’s theorem, 486 Continuous energy spectrum, 24
Cerenkov counter, 571 Coolant, 362
C-fram e of reference, 29, 555 Correspondence principle, 121
Chadwick, J. (1891- ), 354 Cosmic ray, 393
Cham ber, bubble, 572 Coulom b excitation, 28, 320
cloud, 366, 571 Coulom b integral, 158
ionization, 366, 569 Coulom b scattering, 308
spark, 573 Counter, Cerenkov, 571
Chain reaction, 362 G eiger-M iiller, 569
Change o f phase, 490 proportional, 569
molar heat of, 491 scintillation, 565
Characteristic tem perature, for rotation, C ovalen t bond, 198
506 C ovalen t solid, 231
for vibration, 509 C l ’ operation, 410
Charge conjugation, 409 C P T operation, 411
Charge-exchange collision, IS4, 188 Critchficld cycle, 366
Charge reflection, 405 Cross section, 350
C lapeyron ’s equation, 491 differential, 304
Cloud chamber, 366, 571 macroscopic, partial and total, 33, 351
Coefficient o f cubical expansion, 488, scattering, coulomb, 308
515 macroscopic, 272
C o llective rotation, 319 total, 306
C ollective vibration, 319 C rystal, ionic, 232
Collision, inelastic, 27 C rystal lattice, 231
Color center, 276 Curie, 332
Com m utator, 107 Curie, P . (1859-1906) and M . (1867-1934),
Com pound nucleus, 319 332
Com pressibility, adiabatic, 516 Cycle, 468
C om pton, A . (1892-1962), 15 Bethe or carbon, 365
Com pton effect, 15 Carnot, 485, 496
Com pton wavelength, 16 Critchfield or proton-proton, 365
Condon, E. (1902- ), 224 nitrogen, 375
Conduction band, 246 C yclical transform ation, 468
 Index

D a litz diagram , 5(30 Electron-positron pair, 32

Davisson, C. (1881-1958), 36 Elem entary particle, 377
dc B roglie, L . (1892- ), 33 Emission, field, 84
de Broglie wavelength, 33 spontaneous, 95
D eb ye, 199 stimulated, 95, 534
Debye-Scherrer patterns, 35 thermionic, 526
D eb ye temperature, 538 Emission spectrum, 22
D ecay, spontaneous, 386 Em ittance, radiation, 11
D ecay modes o f unstable particles, 386 Energy, binding, 76
D ecay probability, 332 chemical, 466
Degeneracy, 688 conservation o f, 404
essential, 119 dissociation, 76
exchange, 152 equipartition o f, 513
Degeneration, gas, 541 Fermi, 249, 521
Degree Kelvin, 444, 496 internal, 462
Degree o f freedom, 512 io n iz a tio n , 76
Deuterium, 365 m o s t p ro b a b le , 455
Deuteron, 293, 301 quantization of, 65
Diamond, 232 to ta l in te rn a l, 463
Dieteriei equation, 516 ze ro -p o in t, 67
Diffuse series, 173 Energy band, 245, 262
Diffusion, 476 Energy correction, relativistic, 131
Dipole moment, electric, 6 E n e r g y d e n s ity , m o n o ch ro m a tic , 7
magnetic, 289 Energy filte r, 37
Disintegration constant, 330 Energy le v e l, 23, 65
Dissociation, 30 E n e r g y w id th , 44
D is so c ia tio n e n e rg y , 76, 201, 216 E n th a lp y , 474, 504
D is trib u tio n law , B o se-E in stcin , 529 E n tr o p y , 475
F e rm i-D ira c , 521 E n tro p y , id eal gas, 478
M a x w e ll-B o ltz m a n n , 439, 445 E q u a tio n o f state, 469
D o n o r, 266 E q u a tio n o f state, D ie te ric i, 516
D o p p le r sh ift, e lec tro m a g n etic, 45, 51 id eal gas, 495
D o u b let, 87, 139 real gas, 497, 501
D ru d c -L o re n tz th e o ry, 270 system , 495
D u lo n g -P e tit law , 539 van d er W aals, 515
E q u ilib riu m , statistical, 435
E d g e d islocation , 238 therm al, 449
E ffe c tiv e mass, 257 E qu ilib riu m p artition , 440
E fficie n cy o f a therm al engine, 486 E q u ip a rtitio n o f energy, 513
E ffusion, 454 E q u iv a le n t electron term s, table of, 166
E ig h tfo ld w ay, 422 E rro r function, 458
E instein , A . (1879-1955), 12, 533 E ssential degeneracy, 119
E lastic scatterin g, 349 E th an e ( H 3 C — C H 3) molecule, 205
E lectric d ipole, 6 E th yle n e ( H 2 C — C H 2) molecule, 205
E lectrical p e rm ittiv ity , 280 Exchange degeneracy, 152
E lectron , 377 Exchange integral, 158
E lectron capture, 341 E xcita tion , coulom b, 2S
E lectron gas, 522 E xcitation s, collective, 319
Electron pair production, 381 E xcita tion energy, 27
59'2 Index
Exclusion principle, 159
Expansion ratio, 465
E xp ectation value, 100
E xtern al work, 467
F-centers, 276
Ferm i, E. (1901-1954), 343, 519
F erm i-D ira c distribution law, 521
Ferm i energy, 249, 521
F erm i temperature, 522
Ferm i velocity, 273
Ferm ion, 160, 378, 519
Field, electrom agnetic, 4
m atter, 33
F ield electron emission, 84
Fin e structure, 156
Fin e structure constant, 132
F irst law o f therm odynam ics, 467
First-generation star, 370
Fission, 296, 357
spontaneous, 359
F ou rier analysis, 39
F ram e o f reference, center o f mass or
C-frame, 29, 555
laboratory o r /,-frame, 28
Franck, J. (1882- ), 27, 224
Franck-Condon principle, 224
Free electron model, 246
Free energy, G ibbs, 490
H elm h oltz, 489, 490
Free expansion, 478
Fundam ental particle, 345, 377
Fusion, 363
Fusion, heat of, 490
G am m a ray, 320, 329
Gas, electron, 522
phonon, 537
photon, 531
Gas constant, 452
Gas degeneration, 541
Gas therm om eter, constant volum e, 496
Gauge transform ation, 404
G ciger-M u ller counter, 569
G ell-M ann , M . (1929- ), 422
G erade, 192
Germ er, L . (1896- ), 36
Gibbs, J. (1839-1903), 436
G ibbs free energy, 490
Grand partition function, 498
Grand partition function, real gas, 498,
501
G raphite, 236
G raviton , 377
Group velo city, 254, 560
G yrom agn etic ratio, 135
nuclear, 290
spin, 289
H adron, 400
H alf-life, 331
Ila lf-v a lu e thickness, 50
H all effect, 281
H am iltonian, 97
H arm onic oscillator, quantum mechanical,
71
H eat, 464, 466
H eat capacity o f gases, constant pressure,
474, 504
constant volum e, 473, 504
H eat capacity o f solids, 536
IIe a t capacity ratio, 505
H eat of fusion, 490
IIc a t of vaporization, 490
H elicity, 380
H elium -I I, 541
Helium , energy levels of, 156
H elium burning, 369
H elm h oltz free energy, 489, 490
Heisenberg, W . (1901- ), 40
Heisenberg uncertainty principle, 40
H erm ite polynom ial, 103
H crm itian, 97
H ertz, G. (1887- ), 27
H ertz, 11. (1857-1894), 11
H ole, 258
H un d’s rule, 163, 167
H yb rid ization o f w ave functions, 204
H ydrogen atom , 109
H ydrogen, energy levels of, 111
radial w ave functions of, 125
spectrum of, 115
H ydrogen-bond solids, 235
H ydrogen chloride (I I C l) molecule, 2 15 ,21S
H ydrogen (H g ) molecule, 194
H ydrogen molecule ion ( I I 2' ), 183
llyp erch arge, 402
IIy p e rfin e splitting, 325
 Index 593

Ice, 235 j- j coupling, 158

Ideal gas, energy distribution in, 453 Joule effect, 271
Id eal gas entropy, 478 Junction, ]>-n, 266
Ideal monatom ic gas, partition function, 451
Im p act parameter, 304 K aon, 389
Im perfections, 238, 272 Kernel, 171
Im p u rity, 238 K ilocalorie per mole, 226
Independent-particle model, 151 K in etic energy, internal, 463
Inelastic scattering, 349 K lein -G ordon equation, 148
Insulator, 261
In ten sity, w ave m otion, 54 Laguerre polynom ial, associated, 146
Intensive variable, 490 Lam b shift, 142
Interaction, electrom agnetic, 4 L a n d i factor, 143
nuclear, 283, 298 L an gevin ’s formula, 447
residual, 315 Laser, 534
spin-orbit, 139, 312 Lattice, 231
strong, 283 L attice momentum, 255
vibration-rotation, 219 L a ttic e vibration, 240
weak, 345 Laue spot pattern, 35
Internal energy, total, 463 L C A O (linear com bination of atom ic
In terstitial atom , 238 orbitals), 186
Intrinsic con d u ctivity, 265 Lee, 'I'. (1926- ), 406
Intrinsic probability, 438, 519 Legendre polynom ial, 145
Ion, 109 Lepton , 378
Ionic bond, 198 Lepton quantum number, 398
Ionic crystal, 232 L -fram e o f reference, 29
Ionization chamber, 569 Lifetim e, 44
Ion ization energy, 76 average, 95
o f the elements, 159 L in e spectrum, 115
Ion ization potential, 31 Linear absorption coefficient, 33
Ionosphere, 31 L oren tz transform ation, 553
Irreversible transform ation, 470 L-S coupling, 164
Isentropic transform ation, 475 Luminescence, 276
Isobar, 284 Lym an series, 116
Isobaric spin, 400
Isobaric transform ation, 473 M acroscopic cross section, 33, 351
Isobars, nucleon, 423 M acroscopic scattering cross section, 272
Isochoric transform ation, 473 M adclu ng constant, 239
Isom er, 323 M agic number, 311
Isomeric transition, 323 M agn etic dipole moment, 289, 317
Isomerism, islands of, 323 orbital, 132
Isospin, 400 spin, 135
Isotherm al bulk modulus, 488 M agn eton , Bohr, 133
Isotherm al transform ation, 474, 484 nuclear, 289
Isotone, 284 M ain sequence star, 370
Isotope, 284 M aser, 534
Isotopic spin, conservation of, 300 Mass, effective, 257
Isotopic spin rotation, 404 Mass defect, 373
Isotopic spin space, 400 M ass number, 109, 283
 Ί
59'i Indei

M athiessen’s rule, 273 N eu trin o detection experim ent, Cowan-

M a tr ix elements, 101 R ei nes, 345
M a tte r field am plitude, 54 N eutron, 377
M axim um overlap, principle of, 202 discovery of, 354
M ax w ell, J. (1831-1879), 436 N eutron capture, 351
M axw ell-H oltzm an n distribution law, 439, N eutron detector, 570
445 N eutron diffraction, 36
M ax w ell relations, 490 N itro gen cycle, 375
M a x w e ll’s form ula for an ideal gas, 452 Noise, 536
M esic atom , 411, 427 N onconservation o f parity, 408
M eson, 378 N o rm a l modes o f vibration , 219
M eta l, 236, 262 N orm alization , 56, 67
M etastab le state, 121 n-type semiconductor, 266
M ethan e (CI-Li) molecule, 204 N u clear angular momentum, 288
M irro r nuclei, 297 Nu clear binding energy, 293
M O (m olecular orb ital), 186 N u clear g y ro magnetic ratio, 290
M od erator, 362 N u clear interaction, 283
M o la r heat o f change o f phase, 491 N u clear m agnetic dipole m oment, 317
M ole, 452 N u clear magneton, 289
M olecule, 183 N u clear radius, 287
acetylene, 207 Nuclear reaction, 348
am monia, 202 Q of a, 350, 374
benzene, 211 N u clear reactor, 362
beta-carotene, 228 N u clear spin, 288
butadiene, 208 Nucleon, 283
conjugated, 208 Nucleon isobars, 423
ethane, 205 Nucleus, compound, 349
ethylene, 205 daughter, 329
heteronuelear, 197 Nuclide, 283
homonuclear, 192
hydrogen, 194 O hm ’s law, 269
methane, 204 Omega-minus experim ent, 423
oxygen, 197 O perator, 96
sodium chloride, 197 quantum, table, 99
w ater, 202 O ptical pumping, 535
M olecular rotation, 212 O rbital, atom ic, 153
M olecular solid, 235 molecular, 186, 192
M olecu lar vibration, 215 O rbital w ave functions, 153
M orse potential, 199 O rthogonal, 97
M oseley, I L (1887-1915), 181 Orlhohelium , 155
M ossbauer, It. (1929- ), 46 O rthohydrogen, 225
M ossbauer effect, 45 O verlap integral, 191
M u ltip let, 166, 399 O xygen energy levels, 169
M u ltip lic ity, 156, 166 O xygen (O 2) molecule, 197
M u ltip o le transition, 321
M uonium , 427 Pairin g effect, 2S8
Pairin g energy, 297, 315
N e ’eman, Y . (1925- ), 422 P air production, 32, 383
N eu trin o, 343, 377 Parahelium , 155

J
 Index 595

Parahydrogen, 225 Pressure, 464

Param agnetism , Pauli spin, 250 zero-point, 541
Parity, 8 8 , 293, 314, 405 Principal series, 173
nonconscrvation of, 408 Principle o f equipartition o f energy,
P a rity operation, 410 513
Partial w ave, 304 Principle o f maximum overlap, 202
Particle, fundam ental or elem entary, Principles o f quantum mechanics, 98
377 P robability, 55
identical, 436, 519 intrinsic, 438, 519
virtual, 421 state, 519
Partition, equilibrium , 440 transition, 44, 94
most probable, 435 P ro b a b ility density, 55
P artition function, 439 P ro b a b ility of distribution, 434
grand, 498 Production, associated, 402
ideal monatom ic gas, 451 pair, 383
Paschen series, 116 Proper function, 96
Pauli, W . (1900-1958), 159 P roper value, 96
Pen etratin g orbits, 127 Proton, 377
Pfund series, 116 Proton-proton cycle, 366
Phase, change of, 490 p -type semiconductor, 266
Phase shift, 79, 306 p-V diagram, 471
Phase space, 42
Phonon, 243 Q of a nuclear reaction, 350, 374
Phonon gas, 537 Q -ciiuation, 558
Phosphorescence, 277 Quadrupole moment, electric, 290, 325
Photoelectric effect, 12, 526 Quantization, energy, 65
atom ic, 31 Quantum number, baryon, 399
Photofission, 358 lepton, 398
Photographic emulsion, 573 Quark, 420
Photoionization, 31
Photon, 18, 377 R adial Schrodingcr equation, 130
spin o f the, 379 R adial w ave function, 125
virtu al, 421 R adiation , blackbody, 8 , 531
Photon gas, 531 electrom agnetic, 5
Photonuclear reaction, 32, 350 synchrotron, 5
Pion, 377, 388 R adiation em ittance, 11
Planck, M . (1858-1947), 8 R ad iation law, Planck, 9, 532
Planck radiation law, 9, 532 R a d ia tive capture, 31
Plasma, 364 R a d ia tiv e transition, induced and
p-n junction, 266 spontaneous, 532
Positron, 32, 340, 377 R a d ia tive transitions in solids, 274
Positronium , 384 Ram an, C. (1888- ), 220
P oten tial barrier, SO Ram an effect, 220
P oten tial box, 64 Range, 73, 372
two-dim ensional, 103 R a tio o f heat capacities, 505
Poten tial energy, internal, 462 Rayleigh-Jeans law, 48, 545
Poten tial step, 59 R eaction, chain, 362
Poten tial wall, 62 nuclear, 348
P oten tial well, 73 photonuclear, 350
596 Index

Q of a, 350, 374 Sem im etal, 263

stripping, 349 Series, hydrogen, 116
R eactor, fusion, 364 radioactive, 329
nuclear, 362 Sharp series, 173
R ea l gas, equation o f state for a, 497, 501 Shell model, 310
grand partition function o f a, 498, 501 independent-particle, 315
R ed giant, 370 Singlet, 154
R educed mass, 112 Slater, J. (1900- ), 170
R eflection coefficient at a potential step, 63 Sodium, fine structure of, 174
R ela tiv e abundance, 367 Sodium chloride (N a C l) molecule, 197
R elaxation time, 270 Solid, covalent, 231
Residual resistivity, 273 ionic, 232
R esistivity, 269 hydrogen-bond, 235
Resonance, 22, 351, 377, 414 molecular, 235
Resotiance absorption, 45 Sound velocity, 536
R est energy, 554 Space quantization, 118
Richardson-Dushman equation, 527, 544 Spark chamber, 573
R otation , characteristic tem perature of, 506 Spectrum, absorption, 22
kinetic energy of, 213 band, 218
molecular, 212 continuous and discrete, 24, 76
Russell-Saunders coupling, 165 emission, 22
R utherford, E . (1871-1937), 310 line, 122
R y d b e rg c o n s ta n t 1 110 x-ray, 21
Spherical harmonics, 122
Sacku r-Tetrode equation, 478 Spin, electron, 135
Saturation, 296 isobaric or isotopic, 400
Scattering, 349 nuclear, 288
Bragg, 253 Spin gyrom agnetic ratio, 289
coherent or R ayleigh, 221 Spin-orbit interaction, 139, 312
elastic and inelastic, 349 Spin space, isotopic, 400
neutron-proton, 303 Spin w ave functions, 154
Ram an, 221 Splitting, hyperfine, 325
Scattering am plitude, 304, 326 Spontaneous decay, 386
Scattering cross section per center, 273 Spontaneous emission, 95
S chm idt lines, 318 Spontaneous fission, 359
Schrodinger, E. (1887-1961), 56 Spontaneous radiative transition, 532
Schrodinger equation, 56 s-scattering, 307
radial, 130 Star, first-generation, 370
relativistic, 148 main sequence, 370
tim e-dependent, 90 red giant, 370
Scintillation counter, 565 second-generation, 370
S cintillation spectrometer, 567 State, bound and unbound, 112
Second-generation star, 370 equation of, 469
Second law o f thermodynamics, 476 excited and ground, 22
Selection rule, 94, 120 metastable, 121
electric-dipole transition, 168 molecular, 192
Self-consistent field, 435 stationary, 23, 92
Sem iconductor, 261 State probability, 519
n -type and p-type, 266 S tation ary state, 23, 92
 Index 597

S t a t is t ic a l e q u ilib r iu m , 4 35 r a d ia l w a v e fu n c tio n s , 125

S ta tis tic s , B o s e - E in s t e in , 519 r a tio o f h e a t c a p a c itie s , 5 14
F e r m i- B ir a c , 519, 522 r o t a t io n a l a n d v ib r a t io n a l c o n s ta n ts in
M a x w e ll- B o lt z m a n n , 436 d ia t o m ic m o le c u le s , 213
S te fa n , J . (1 8 3 5 - 1 8 9 3 ), I l R y d b e r g c o n s ta n t, 112
S t e fa n - B o lt z m a n n la w , 11 s t a b le a n d lo n g - liv e d n u c lid e s , 315
S te r n - G e r la c h e x p e r im e n t , 135 s tra n g e n e s s o f m e so n s a n d b a r y o n s , 400
S tim u la t e d e m is s io n , 95, 534 te r m s f o r e q u iv a le n t e le c tr o n s , 166
S t ir lin g ’s fo r m u la , 4 40, 563 th e r m io n ic c o n s ta n t, 527
S to k e s lin e, 221 th re s h o ld e n e r g ie s f o r p h o to fis s io n , 358
S tra n g e n e s s , 402 u r a n iu m serie s , 331
S t r ip p in g r e a c tio n , 349 v a n d e r W a a ls c o n s ta n ts , 503
S t r o n g in te r a c tio n , 283 v ib r a t io n a l e n e r g y le v e ls o f N H s
m o le c u le , 87
T a b le , a n g u la r m o m e n tu m s ta t e w a v e fu n c t io n s o f a h a r m o n ic o s c illa t o r ,
d e s ig n a tio n s , 118 72
a n g u la r w a v e fu n c tio n s , 123 w o r k fu n c t io n , 527
b o n d le n g th s in d ia t o m ic m o le c u le s , 199 T e m p e r a t u r e , 495
c h a r a c te r is tic t e m p e r a tu r e fo r a b s o lu te , 444, 482
r o ta tio n , 508 B o y le , 515
c h a r a c te r is tic te m p e r a tu r e f o r v ib r a t io n , c h a r a c te r is tic , fo r r o t a t io n , 506
508 f o r v ib r a t io n , 509
D e b y e te m p e r a tu r e s , 538 D e b y e , 538
d is s o c ia tio n e n e r g ie s in d ia to m ic F e r m i, 5 22
m o le c u le s , 199 m e a s u r e m e n t o f, 495
e ff e c t iv e m ass, 257 n e g a t iv e a b s o lu te , 483
e le c t r ic d ip o le m o m e n ts in d ia to m ic t h e r m o d y n a m ic , 497
m o le c u le s , 199 T e r m , 165
e le c tr o n ic c o n fig u r a tio n s o f a t o m s , 162 m o le c u la r g ro u n d s ta te , 2 0 0
e le c tr o n ic c o n fig u r a tio n s o f h o m o n u c le a r T h e r m a l e n g in e e ffic ie n c y , 486
d ia t o m ic m o le c u le s , 196 T h e r m a l e q u ilib r iu m , 449
e le c tr o n ic s ta t e d e s ig n a tio n s , 139 T h e r m a l n e u tro n s , 37
e n e r g y c o r r e c tio n f o r n u c le a r m o tio n , 115 T h e r m a l o s c illa t o r y m o tio n , 372
e n e r g y le v e ls a n d d e g e n e r a c ie s in a T h e r m io n ic e m is s io n , 526
c u b ic a l b o x , 69 T h e r m o d y n a m ic s u rfa c e , 469
e n e r g y g a p s , 265 T h e r m o d y n a m ic te m p e r a tu r e , 497
e r r o r fu n c t io n , 459 T h e r m o d y n a m ic s , 462
e s s e n tia l d e g e n e r a c y , 118 fir s t la w o f, 467
F e r m i e n e r g y , 249, 524 s e c o n d la w o f, 476
F e r m i te m p e r a tu r e , 524 z e r o t h la w o f, 449
fis s io n a b ilit y o f h e a v y n u c lei, 358 T h e r m o m e t e r , 495
fu n d a m e n ta l p a rtic le s , 378 g a s , 4 96
h y p e r c h a r g e a n d is o t o p ic s p in o f m eso n s T h o m s o n , G . (1 8 9 2 - ) , 35
a n d b a ry o n s , 400 T h o r iu m serie s , 329
p a r t ic le d e c a y m o d es , 387 T h r e s h o ld e n e r g y , 393
p r o p e r tie s o f fis s io n a b le m a te ria ls , 360 T h r e s h o ld k in e tic e n e r g y , 28
p r o p e r tie s o f n u c lid e s , 291 T ig h t - b i n d in g a p p r o x im a t io n , 259
q u a n tu m o p e r a to r s , 99 T i m e , re la x a t io n , 270
Q -v a lu e fo r d iff e r e n t 232U d e c a y s , 340 T i m e r e v e r s a l, 410
598 Index

Time translation, 404 lattice, 240

Transformation, adiabatic, 474, 484 molecular, 215
cyclical, 468 normal modes of, 219
irreversible, 470 solid collective, 536
isentropic, 475 Vibrational energy, zero-point, 200, 216
isobaric, 473 Vibrational excited state, nuclear, 320
isochoric, 473 Vibrational-rotational transitions, 217
isothermal, 474, 484 Virial coefficients, 497
reversible, 470 Virtual particle, 421
Transition, electric dipole, 94
electronic, in molecules, 222 Water (H 2 O) molecule, 202
isomeric, 323 vibrational levels in, 220
multipole, 321 Wave function, 54
vibration-rotation, 217 angular, 123
Transition probability, 44, 94 antibonding and bonding, 187
induced emission, 533 determinantal, 160
radiative, 321 molecular, 192
spontaneous, 533 normalization and orthogonality of, 67
Transport phenomena, 476 parity of, 125
Trap, 277 Wave number, 58, 115
Tritium, 365 Wave packet, 38, 58
Turning point, classical, 75 Weak boson, 422
Weak interaction, 345
Uncertainty principle, Heisenberg, 40 Weiszacker formula for nuclear binding
Undetermined multipliers, Lagrange, 441, energy, 296
564 Wein, W. (1864-1928), 10
Ungerade, 192 Wein displacement law, 10
Unified model of the nucleus, 316 Work, 463
Uranium series, 329 Work function, 13, 249, 526
W-particle, 377
Valence band, 246 Wu, C. (1913- ), 407
Valence electron, 171
van der Waals constants, 503 X-ray, characteristic, 176
van der Waals force, 235 X-ray diffraction, 36
Vector, axial and polar, 405 X-ray emission in solids, 274
Velocity, average, 455
cen*ter of mass, 29 Yang, C. (1922- ), 406
Fermi, 273 Yukawa, H. (1907- ), 300, 388
group, 38, 254, 560 Yukawa potential, 299
most probable, 455
phase, 38 Zeeman, P. (1865-1943), 132
. root-mean-square, 455 Zeeman effect, 132
Velocity of sound, 536 Zener effect, 257
Velocity selector, 454 Zeroth law of thermodynamics, 449
Vibration, characteristic temperature for. Zero-point energy, 67, 72
509 Zero-point pressure, 541