SEVENTHEDITION

Introductionto
SolidStatePhysics
CHARLES KITTEL
14
Diamagnetism and Paramagnetism
LANGEVIN DIAMAGNETISM EQUATION 417
QUANTUM THEORY OF DIAMAGNETISM OF
MONONUCLEAR SYSTEMS 419
PARAMAGNETISM 420
QUANTUM THEORY OF PARAMAGNETISM 420
Rare earth ions 423
Hund rules 424
Iron group ions 425
Crystal field splitting 426
Quenchingofthe orbital angular momentum 426
Spectroscopie splitting factor 429
Van Vleck temperature-independent paramagnetism 430
COOLING BY ISENTROPIC DEMAGNETIZATION 431
Nuclear demagnetization 432
PARAMAGNETIC SUSCEPTffiILITY OF
CONDUCTION ELECTRONS 433
SUMMARY 436
PROBLEMS 436
1. Diamagnetic susceptibility ofatomic hydrogen 436
2. Hund rules 437
3. Triplet excited states 437
4. Heat capacity from internaI degrees offreedom 438
5. Pauli spin susceptibility 438
6. Conduction electron ferromagnetism 438
7. Two-Ievel system 440
8. Paramagnetism ofS =1 system 440
REFERENCES 440
NOTATION: In the problems treated in this chapter the magnetic field B is always
closely equal to the applied fiel d Ba, so that we write B for Ba in most instances.
--------
t
+
r ~ T _
Pauli paramagnetism (metals) Temperature
Diamagnetism
Figure 1 Characteristic magnetic susceptibiliti es of diamagnetic and paramagnetic substances.
416
CHAPTER 14: DIAMAGNETISM AND PARAMAGNETISM
Magnetism is inseparable from quant um mechanics, for a strictly classical
system in thermal equilibrium can display no magnetic moment, even in a
magnetic field . The magnetic moment of a free atom has three principal
sources: the spin with which electrons are endowed; their orbital angular mo-
mentum about the nucleus; and the change in the orbital moment induced by
an applied magne tic field.
The first two effects give paramagnetic contributions to the magnetization,
and the third gives a diamagnetic contribution. In the ground Is state of the
hydrogen atpm the orbital moment is zero, and the magnetic moment is that of
the electron spi n along with a small induced diamagnetic moment. In the 1S2
state ofhelium the spin and orbital moments are both zero, and there is only an
induced moment. Atoms with filled electron shells have zero spin and zero
orbital moment: these moments are associated with unfilled shells.
The magnetization M is defined as the magnetic moment per unit volume.
The magnetic susceptibility per unit volume is defined as
M
(SI) X = /-LoM
(1)
(CeS) x = 13 '
B
where B is the macroscopic magne tic field intensity. In both systems of units X
is dimensionless. We shall sometimes for convenience refer to MIB as the sus-
ceptibility without specifying the system of units .
Quite frequently a susceptibility is defi ned referred to unit mass Or to a
mole of the substance. The molar susceptibility is written as XM ; the magnetic
moment per gram is sometimes writt en as CT. Substances with a negative mag-
netic susceptibility are called diamagnetic. Substances wit h a positive suscepti-
bility are called paramagnetic, as in Fig. 1.
Ordered arrays of magnetic moments are discussed in Chapter 15; the
arrays may be ferromagnetic, ferrimagnetic, antiferromagnetic, helical, or
more complex in for m. Nuclear magnetic moments give rise to nuclear
3
paramagnetism. Magnetic moments of nuclei are of the order of 10- times
smaller than the magnetic moment of the electron.
LANGEVIN DIAMAGNETISM EQUATION
Diamagnetism is associated with the tendency of electrical charges par-
tially to shield the interior of a body from an applied magnetic field. In electro-
magnetism we are familiar with Lenz's law: when the fl ux through an electrical
circuit is changed, an induced current is set up in such a direction as to oppose
the flux change.
417
418
In a superconductor or in an electron orbit within an atom, the induced
current persists as long as the fi eld is present. The magnetic field of the induced
current is opposite to the applied field, and the magnetic moment associated
with the current is a diamagnetic moment. Even in a normal metal there is a
diamagnetic contribution from the conduction electrons, and this diamag-
netism is not destroyed by collisions of the electrons.
The usual treatment of the diamagnetism of atoms and ions employs the
Larmor theorem: in a magnetic field the motion of the electrons around a
central nucleus is , to the first order in B, the same as a possible motion in the
absence of B except for the superposition of a precession of the electrons with
angular frequency
(ces) w = eB/2mc (SI) w = eB/2m . (2)
If the field is applied slowly, the motion in the rotating reference system will be
the same as the original motion in the rest system before the application of the
field.
If the average electron current around the nucleus is zero initially, the
application of the magnetic fi eld will cause a finite current around the nu-
cleus. The current is equivalent to a magnetic moment opposite to the applied
field. It is assumed that the Larmor frequency (2) is much lower than the fre-
quency of the original motion in the central field. This condition is not satisfied
in free carrier cyclotron resonance, and the cyclotron frequency is twice the
frequency (2).
The Larmor precession of Z electrons is equivalent to an electric current
1 eB)
(SI) 1 = (charge)(revolutions per unit time) = (- Ze)
(
- . -- . (3)
271' 2m
The magnetic moment I.L of a current loop is given by the product
(current) X (area of the loop). The are a of the loop of radius p is 7TP'2. We have
ZtfB
(SI)
JI. =- 4m (p'l) ;
(4)
Here (p'2) = (x'2) + (y'2) is the mean square of the perpendicular distance of the
electron from the fiel d axis throtigh the nucleus. The mean square distance of
the electrons from the nucleus is (r'2) = (x
2
) + (y2) + (Z2). For a spherically
symmetrical dist ribution of charge we have (x
2
) = (y2) = (Z2), so that (r
2
) =
i(p2).
From (4) the diamagnetic susceptibility per unit volume is, if N is the
number of atoms per unit volume,
2
= NI.L = _ NZe (r'2)
(ces)
X
(5)
B 6mc'2 '
419 14 Diamagnetism and Paramagnetism
2
x = ILQNIl- = ILQNZe (r
2
)
(SI)
B 6m
This is the classical Langevin result.
The problem of calculating the diamagnetic susceptibili ty of an isolated
atom is reduced to the calculation of (r
2
) for the electron distribution within the
atom. The distribution can be calculated by quantum mechanics .
Experimental val ues for neutral atoms are most easily obtained for the
inert gases. Typical experimental values of the molar susceptibilities are the
following:
He Ne Ar Kr Xe
XM in CGS in 10-
6
cm
3
lrnole: -1.9 -7.2 -19.4 -28.0 -43.0
In dielectric solids the diamagnetic contribution of the ion cores is de-
scribed roughly by the Langevin result. The contribution of conduction elec-
trons is more complicated, as is evident from the de Haas-van Alphen effect
discussed in Chapter 9.
QUANTUM THEORY OF DIAMAGNETISM OF MONONUCLEAR SYSTEMS
From (G. 18) the effect of a magnetic field is to add to the hamiltonian the
terms
ieh e
2
A
2
J-C = -(V' . A + A V') + -- , (6)
2mc 2mc
2
for an atomic electron these tenns may usually be treated as a small perturba-
tion. If the magnetic field is uniform and in the z direction, we may write
A x = ~ y B , Ay = h B , Az = 0 , (7)
and (6) becomes
2
iehB(d d) e
2
B
J-C = -- x- - y- + --(x
2
+ y2)
(8)
2mc dy dx 8mc
2
The first term on the right is proportional to the orbital angular mUlnen-
tum component Lz if r is measured from the nucleus. In mononuclear systems
this term gives rise only to paramagnetism. The second term gives for a spheri-
cally symmetric system a contribution
2 2
E' = e B
2
-12 (r )
(9)
n1C
2
'
The moment is
netic:
in with
ta is in:
lar oxygen and organic """<'>,","'0
4. Metals<
The moment of an atom or ion in free space is given
where the total angular momentum IiL and liS
angular momenta<
The constant 1's the ratio of the moment to the angular momen-
tum; l' is called the
a g
defined by
For an g = 2. as For a free atom the g
factor is the Land equation
g = l +
421 14 Diamagnetism and Paramagnetism
4 s:: 1.00
1
ms IJ.z
1
0
.
75
0.
8.
0
.
50
'If
.02
( /// 2ILB - IL
"
s::
B025
--', 1
e
c....
". -2 !J. o1 I ii 1
o 0.5 1.0 1.5 2.0
ILBlkBT
Figure 2 Energy level splitting for one electron
in a magnetic field B directed along the positive z Figure 3 Fractional populations of a two-level
axis. For an electron the magnetic moment JL is system in thermal equilibrium at temperature T
opposite in sign to the spin S, so that JL = in a magnetic field B. The magnetic moment is
-gJLBS. In the low energy state the magnetic proportional ta the difference between the two
moment is paraIJel ta the magnetic field. curves.
The Bohr magneton J-tB is defined as eh/2mc in ces and eh/2m in SI. It is
closely equal to the spin magnetic moment of a free electron.
The energy levels of the system in a magnetic field are
U = - P' B = mjgJ-tBB , (14)
where mj is the azimuthal quantum number and has the values J, J - l, ... ,
- J. For a single spin with no orbi tal moment we have mj = i and g = 2,
whence U = J-tBB. This splitting is shown in Fig. 2.
If a system has only two levels the equilibrium populations are, with
T == kBT,
NI
exp(J-tBIT)
(15)
N
exp(j.LBiT) + exp( - j.LBIT) ,
N
z
exp( - J-tB IT)
(16)
N exp(J-tBIT) + exp( - j.LBiT) ,
here N
j
, N
z
are the populations of the lower and upper levels, and
N = N
j
+ N
2
is the total number of atoms. The fractional populations are plot-
ted in Fig. 3.
The projection of the magnetic moment of the upper state along the field
direction is - J-t and of the lower state is J-t. The resul tant magnetization for N
atoms per unit volume is , with x == J-tB/kBT,
eX - e-
X
M = (NI - N
2
)J-t = NJ-t x + _, = NJ-t tanh x .
(17)
e e
For x l , tanh x = x, and we have
M =NJ-t(J-tB/kBT)
(18)
In a magnetic field an atom with angular momentum quantum number J
has 2J + 1 equally spaced energy levels. The magnetization (Fig. 4) is given by
M = NgJJ-tB Bj(x) , (x == gJJ-t BB/k
B
T) ,
(19)
422
7.00
BIT in kG deg- L
Figure 4 Plot of magnetic moment versus BIT for spherical samples of (1) potassium chromium
alum, (II) ferric ammonium alum, and (III) gadolinium sulfate octahydrate. Over 99.5% magnetic
saturation is achieved at 1.3 K and about 50,000 gauss. (ST). After W. E. Henry.
where the Brillouin function BI is defined by
2J + 1 ((2J + l)x) 1 ( x )
B,(x) = ctnh - - ctnh - (20)
. 2J 2J 2J 2J
Equation (17) is a special case of (20) for J = t.
For x <s:; l, we have
1 x x
3
ctnh x = - + - - - + (21)
x 3 45
and the susceptibility is
M NJ(J + C
-=
(22)
B 3k
B
T T
Here p is the effective number of Bohr magnetons, defined as
p == gU(J + 1)F
/2
. (23)
14 Dianwgnetism and Paranwgnetism
4 0 ~ - - - - - - - - ~ - - - - ~ ~ - ~ - - - - - - ~ ~
s
i
Temperature, Je
Figure 5 Plot of l/X vs T for a gadolinium salt, Gd(C
z
H
5
S0
4
h . straight line the
Curie law, (Aftel' L. C. Jackson and Onnes,)
Rare Earth Ions
Even in the
no other
atom
state is charac-
maximum S allowed exclusion
maximum value of the momentum consistent with
of S,
is to IL - SI when the
shell is more than half fulL
ruIe L 0, so
different
425 14 Diamagnetism and Paramagnetism
Table l Effective magneton numbers p for trivalent lanthanide group ions
(Near room tempe rature)
----
p(calc) = p(exp),
Ion Configuration Basic level gU(] + 1)]JJ2 approximate
__.=:l
c +
4P5s
2
p6
2F
s I2
2. 54 2.4
Pr
3
+
4j25s
2
p6
3H
4
3. 58 3. 5
Nd
3
+
4P5s
2
p6
41
912
3.62 3.5
Pm
3
+
4f
4
5s
2
p6
51
4
2. 68
Sm
3
+
4f
s
5s
2
p 6
6H
sf2
0.84 1.5
Eu3+
4f
6
5s
2
p6
7F
o
0 3.4
Gd
3
+
4F5s
2
p6
8S
712
7.94 8.0
Tb
3
+
4j'B5s
2
p6
7F
6
9.72 9.5
D
y
3+
4f
9
5s
2
p6
6H
1SI2
10.63 10.6
Ho
3
+ 4po5s
2
p6 s Is
10.60 10.4
Er
3
+ 4f1l5s
2
p6
41
1S12
9.59 9.5
Tm
3
+
4P
2
5s
2
p6
3H
6
7. 57 7.3
Yb
3
+
4P
3
5s
2
p6
2F7i2
4.54 4.5
The second Hund rule is best approached by model calculations. Pauling
and Wilson, l for example, give a calculation of the spectral terms that arise fro m
the configuration p2. The third Hund rule is a consequence of the sign of the
spin-orbit interaction: For a single electron the energy is lowest when the spin
is antiparallel to the orbital angular momentum. But the Iow energy pairs mL,
ms are progressively used up as we add electrons to the shell; by the exclusion
principle when the shell is more th an half full the state of lowest energy neces-
sarily has the spin parallel ta the orbit.
Consider two examples of the Hund fuIes: The ion c + has a single f
electron; an f electron has l = 3 and s = i. Because the f shell is less than half
full, the ] value by the preceding rule is IL - SI = L - ! = l The ion Pr
3
+ has
two f electrons: one of the mIes tells us that the spins add to give S = 1. Both f
electrons cannot have ml = 3 without violating the Pauli exclusion principle, so
that the maximum L consistent with the Pauli principle is not 6, but 5. The]
value is IL - si = 5 - 1 = 4.
Iron Group Ions
Table 2 shows that ~ h experimental magneton numbers for salts of the iron
transition group of the pelt'iodic table are in poor agreement with (18). The
values often agree quite weil with magneton numbers p = 2[S(S + 1)]112 calcu-
IL. Pauling and E. B. Wilson, Introduction to quantum mechanics, McGraw-Hill, 1935,
pp. 239-246.
426
Table 2 Effective magneton numbers for iron group ions
Config- Basic p(calc) = p(calc) =
Ion uration level gU(] + 1)]112 2[$($ + 1)]112 p(exp)a
Ti3+, y4+
3d
l
2D
3I2
1.55 1.73 1.8
y3+
3d
2
3F
2
1.63 2.83 2.8
Cr3+, y2+
3d
3
4F
3
/
2
0.77 3.87 3.8
Mn
3
+, Cr+
3d
4
5DO
0 4.90 4.9
Fe
3
+, Mn
2
+
3d
5
65
51 2
5.92 5.92 5.9
Fe
2
+
Co
2
+
3d
6
3d
7
5D
4
4F
9
/
2
6.70
6.63
4.90
3.87
5.4
4.8
Ni
2
+
3d
8
3F
4
5.59 2.83 3.2
Cu
2
+
3d
9
2D
5
/
2
3.55 1.73 1.9
"Representative values.
lated as ifthe orbital moment were not there at ail. We say that the orbital
moments are quenched.
Crystal Field Splitting
Thedifferencein behavioroftherareearthand theirongroupsaltsis that
the 4f shell responsible for paramagnetism in the rare earth ions lies deep
inside theions, within the 5s and5p sheIls, whereasin the iron group ions the
3d shell responsible for paramagnetism is the outermost shell. The 3d shell
experiencestheintenseinhomogeneouselectricfield producedbyneighboring
ions. This inhomogeneouselectricfield is called the crystalfi eld.Theinterac-
tion ofthe paramagnetic ions with the crystal fi eld has two major effects: the
couplingofLandSvectorsis largelybrokenup, sothatthestatesarenO longer
specifiedbythei r J values;further, the2L + l sublevelsbelongingtoagivenL
whicharedegeneratein thefree ion may nOw besplitbythecrystalfield,as in
Fig. 6. This split ting diminishes the contribution ofthe orbital motion to the
magnetic moment.
Quenching of the Orbital Angular Momentum
Inan electricfield directed toward afixed nucleus, theplaneofaclassical
orbitisfixedin space, sothataIl theorbitalangularmomentumcomponentsLx>
Ly, Lzare constant. In quantum theory one angular momentum component,
usually takenas Lz, andthesquareofthetotalorbitalangularmomentumL
2
are
constantin acentralfield. Inanoncentralfield the planeofthe orbitwill move
about; the angular momentum components are no longer constant and may
average to zero. In a crystal Lz will no longer be a constant of the motion,
although to a good approximation L
2
may continue to be constant. When Lz
averages to zero, the orbital angular momentum is said to be quenched. The
427 14 Diamagnetism and Paramagnetism
@ @ @
===== P"Py
y
- ---pz
y
@

(a) (b) (c) (d)
Figure6 Consideran atomwithorbitalangularmomentumL = l placedin theuniaxialcrystalline
electricfield ofthe two positive ions along thez axis. In thefree atom the states mL = l, 0have
identical energies-they are degenerate. In the crystal the atom has a lower energy when the
electron cloudis close to positive ions as in (a) than when it is oriented midway between them, as
in (b) and (c). The wavefunctions thatgive rise to thesecharge densitiesareoftheform zf(r), xf(r)
and yf(r) and arecalled thePz, Px, Py orbitaIs, respectively. Inan axially symmetricfield, as shown,
thePx and Py orbitaIs are degenerate. The energylevels referredto thefree atom (dotted!ine)are
shown in (d). If the electricfield does not have axial symmetry, ail three stateswill have different
energies.
magnetic moment of astate is given by the average value of the magnetic
moment operator I-t B(L + 2S). In a magnetic field along the z direction the
orbital contribution to the magnetic moment is proportional to the quantum
expectation value ofL z; the orbital magnetic moment is quenched ifthe me-
chanical moment Lzis quenched.
When the spin-orbit interaction energy is introduced, the spin may drag
sorne orbitalmomentalongwithit. If thesignofthe interaction favors paraUel
orientation of the spin and orbital magnetic moments, the total magnetic mo-
mentwill belargerthanforthespinalone, and thegvaluewillbelargerthan2.
The experimentalresults are in agreementwith theknown variation ofsign of
thespin-orbitinteraction:g > 2whenthe 3d shellis more than halffull,g = 2
when the shell is halffull , and g < 2 when the shell is less than halffull .
Weconsiderasingleelectronwi thorbitalquantumnumberL = 1moving
aboutanucleus, the wholebeingplacedin aninhomogeneouscrystallineelec-
tric field. We omit electron spin.
In a crystal oforthorhombic symmetry the charges on neighboring ions
will produce an electrostatic potential cp about the nucleus ofthJ form
ecp = AX2 + B
y
2 - (A + B )Z2 , (24)
whereA and B are constants. This expression isthe lowestdegree polynomial
in x, y, z which is a solution ofthe Laplace equation V
2
cp = 0 and compatible
with the symmetry ofthe crystal.
428
U
y
= yf(r) ; U
z
= zf(r)
are normalized.
= 2U
i
,
= 0 .
Consider
dx dy dz ; (28)
the integral
the diagonal matrix
elements:
+
dx dy dz
(29)
where
dx dz ;
The their angular lobes
o.
This effect is
momentum,
age is zero in
magnetic moment also
Paramilgnetttm
(30)
- /
l
,
the hetween
g
g
1966; extensive 'See L. Orgel, Introduction to transition
references are given by D. Sturge, Phys.
430
Van Vleck Temperature-Independent Paramagnetism
We consider an atomic or molecular system which has no magnetic mo-
ment in the ground state, by which we mean that the diagonal matrix element
of the magnetic moment operator J.Lz is zero.
Suppose that there is a nondiagonal matrix element (slJ.LzIO) of the magnetic
moment operator, connecting the ground state with the excited state s of
energy = Es - Eo above the ground state. Then by standard perturbation
theory the wavefunction of the ground state in a weak field (J.LzB ) becomes
(32)
and the wavefunction of the excited state becomes
(33)
The perturbed ground state now has a moment
(34)
and the upper state has a moment
(35)
There are two interesting cases to consider:
Case (a). kBT. The surplus population in the ground state over the
excited state is approximately equal to N/2k
B
T, so that the resul tant magneti-
zation is
M = 2BI(slJ.LzIO)1
2
N
(36)
2k
B
T '
which gives for the susceptibility
(37)
Here N is the number of molecules per unit volume. This contribution is of the
usuaI Curie form, although the mechanism of magnetization here is by polariza-
tion of the states of the system, whereas with free spins the mechanism of
magnetization is the redistribution of ions among the spin states. We note that
the splitting does not enter in (37).
Case (h) . ;? kBT. Here the population is nearly aIl in the ground state, so
that
M = 2NBI(slJ.LzIO>1
2
(38)

The susceptibility is
(39)
431 Diamagnetism P aramagnetism
type of contribution known as Van Vleck
COOLING DY
The first metbc,d
the
partly lined
is also lowered if
1) .
in
3The method was suggested by P Debye, Ann. Giauque,
Am, Chem, Soc, 49, 1864 (1927). For many purposes by the
dilution which operates solution in
He' play the raIe of atoms in a gas, and
12.
432
Spi n
Total
Spin
Latti ce Time-
Time-
Before 1 New equili brium Beore :\cw equilibrium
Time at which Time at which
magnetic fi eld magnetic field
is removed
is l' emoved
Figure 7 During adiabatic demagnetization the total entropy of the specimen is constant. For
effective cooli ng theiniti alentropyofthelatticeshouldbesmall in comparison with theentropyof
the spi n system.
Thestepscarriedoutin the coolingprocessareshown in Fig. 8. Thefield
is applied at temperature Tl with the specimen in good thermal contact with
the surroundings, giving the isothermal path ab. The specimen is then insu-
lated (!la- = 0) and the fi eld removed; the specimen follows the constant en-
tropypath he, ending up at temperature T
2
. Thethermal contact atTl is pro-
vided by helium gas, and the thermal contact is broken by removing the gas
with a pump.
Nuclear Demagnetization
The populati on ofa magnetic sublevel is afunction onlyoff.LBl kBT, hence
ofBIT. The spin-system entropy is a function only ofthe population distribu-
tion;hencethespinentropyis afunctiononlyofBIT. If Bt>. is theeffectivefield
that corresponds to the local interactions, thefinal temperature T
2
reached in
an adiabatic demagnetization experiment is
1 1 T2 = Tl (Bt>.IB) ,
(41)
whe re B is the initial fi eld and Tl the initial temperature.
Because nuclear magnetic moments are weak, nuclear magnetic interac-
tions aremuch weakerthan similarelectronicinteractions.Weexpectto reach
atemperature100timeslowerwithanuclearparamagnet thanwithanelectron
paramagnet. The initial temperature Tl ofthe nuclear stage in a nuclearspin-
coolingexperimentmustbe lowerthaninan electronspin-coolingexperiment.
If we start at B = 50 kG and Tl = 0.01 K, then f.LBlkBT
l
= 0.5, and the en-
433 14 Diamagrwtism and Paramagfletism
B =0; BA =100 gauss

0.6


0.5

S

g

0. 3

S Qi

0.1
o6 L 10 15 do j'J
T, mK
'igure 8 Entropy for a , pin 1sys tem as a funetion of te mperature, assuming an internaI random
magne tic field Be:. of 100 gauss. The specimen is magnetized isothermall y along ab , and is th en
insulated thermally. The external magnetie field is turned off al ong be. In order to keep the figure
on a reasonable seale the initial temperature Tl is lower th an wouId be used in practice, and so is
the external magnetic fi eld.
tropy decrease on magnetization is over 10 percent of the maximum spin en-
tropy. This is suffici ent to overwhelm the lattice and from (41) we esti mate a
final temperature T
2
= 10-
7
K. The first
4
nuclear cooling experiment was car-
ried out on Cu nudei in the metal, starting from a fi rst stage at about 0.02 K
as attained by electronic cooli ng. The lowest temperature reached was
1.2 x 10-
6
K.
The results in Fig. 9 fit a line of the fonn of(41) : T
z
= T
1
(3.1/B) wi th B in
gauss, so that B11 = 3.1 gauss. This is the effective interaction field of the mag-
netic moments of the Cu nuclei. The motivation for using nud ei in a metal is
that conduction electrons help ensure rapid thermal contact of lattice and nu-
dei at the tempe rature of the first stage. The present record
5
for a spin temper-
ature is 280 pK, in rhodium.
PARAMAGNETIC SUSCEPTIBILITY OF CONDUCTION ELECTRONS
We are going to try to show how on the basis of these stati sti cs the fact that many
metals are diamagneti c, or only weakl y paramagnetic, can be brought into agree-
ment with tbe existence of a magneti c mome nt of tbe electrons .
W. Pauli, 1927
Classical fr ee electron theory gives an unsatisfactory account of the para-
magnetic susceptibility of the conduction electrons. An electron has associated
with it a magnetic moment of one Bohr magneton, /-La. One might expect that
4N. Kurti , F. N. H. Robinson, F. E. Simon, and D. A. Spohr, Nature 178, 450 (1956); for
reviews see N. Kurti, Cryogenies 1, 2 (1960); Adv. in Cryogenie Engineering 8, 1 (1963).
sp. J. Hakonen et al ., Phys . Rev. Lett. 70, 2818 (1993).
434
Initial magnetic field in kG

9
8
7
1 6
5
1;0
.,
e 4
u

.S 3
lL-__
0.3 0.6 2
Initial BIT in 10
6
G/K
Figure 9 Nuclear demagnetizations ofcopper nuclei in the metal, starting from 0.012 K and
various fields. (After M. V. Hobden and N. KurtL)
the conduction electrons would make a Curie-typeparamagnetic contribution
(22) to the magnetization ofthe metal: M = Instead it is observed
thatthemagnetizationofmostnormal nonferromagneticmetals is independent
oftemperature.
Pauli showed that the application ofthe Fermi-Dirac distribution (Chap-
ter6)w6uld correctthetheoryas required. Wefirst giveaqualitativeexplana-
tionofthesituation.Theresult(18) tellsusthattheprobabili ty anatomwillbe
linedupparallel to thefield Bexceeds theprobabilityoftheantiparallelorien-
tation by roughly /-LBlkB T. For N atoms perunitvolume, this gives a net mag-
netization = N/-L2Bl k
B
T, the standard result .
Most conduction electrons in a metal, however, have no possibility of
turning over when a fiel d is applied, because most orbitais in the Fermi sea
with parallelspin are alreadyoccupied. Only theelectrons withina range kBT
ofthetopoftheFermidistribution haveachanceto turnoverin thefield; thus
onlythefractionTIT F ofthetotal numberofelectronscontributeto thesuscep-
tibility. Hence
N/-L2B T N/-L2
M =--' -=--B
kBT TF kBT
F
which is independentoftemperatureand oftheobserved orderofmagnitude.
We now calculate the expression for the paramagnetic susceptibility of a
free electrongas atT TF. We follow the methodofcalculation suggestedby
Fig. 10. An alternate derivation is the subject ofProblem 5.
--
435 14 Diamagnetism and Paramagnetism
Total energy, kinetic +
magnetic, ofelectrons
l 1 ~
Parallel
ta field
, D f f i ~ ~ ~
.... ~ Density of
1 orbitais < o ~ ~
1
(a)
(b)
Figure 10 Pauli paramagnetism at absolute zero; the orbitais in the shaded regions in (a) are
occupied.Thenumbersofelectrons in the"up"and "down" bandwill adjust ta make theenergies
equal at theFermilevel. Thechemicalpotential(Fermilevel) ofthe momentup electronsis equal
to that ofthe moment down electrons. In (b) we show the excess ofmoment up electrons in the
magnetic field.
The concentration of electrons with magnetic moments parallel to the
magnetic fiel d is
l J'F l lEF l
N+ = - dED(E + fJ-B ) == - dED(E) + - fJ-B D(EF) ,
2 - l'-B 2 0 2
written for absolute zero. Here~ D E + fJ-B ) is the densitv oforbitaIs ofone
:2
spin orientation, with allowance for the downward shift ofenergy by - fJ-B .
Theapproximation iswrittenfor kBT <{ E
F

The concentration ofelectrons wi th magnetic moments antiparallei to the
magnetic field is
l JEF l l l'F
N_ = - dE D(E- fJ-B) == - dE D(E) - - fJ-B D(EF)
21'-B 20 2
The magnetization is given by M = fJ-( N + - N _), so that
3N fJ- 2
M = fJ-2 D (EF) B = - k B (42)
2 BT
F
with D(EF) = 3N/2EF = 3N/2k
B
T
F
from Chapter 6. The result (42) gives the
Pauli spinmagnetizationoftheconduction electrons, for kBT <{ E
F

In deriving the paramagnetic susceptibility, we have supposed that the
spatial motion of the electrons is not affected by the magnetic field. But the
wavefunctions are modifi ed by the magnetic field; Landau has shown that for
436
B.
..
..
(43)
the
by
The
UUU1H.l<U.'y high for transition
heat
of atomic Z is X
atomic (Langevin)
the maximum S
consistent with this S. The
and IL - S if the shell is Jess
is
437 14 Diamagnetism andParamagnetism
8 0
r iT T T
tS 1 1 1 IIT-
7.0
6.0

5.0

\
\ -r--r-2_
w
E
"
\
1
8
Cr
__ 4.0
"
\ // ......V
g

0.
'"
:l
"
V>

3.0
'\
f-- - r--_ "-
2.0
Ir- --

_J-_+-_r-zr- v - -
_ Rh
l
1'1
1.0
Na
'"
K--
-+--1f--+_-J-::
Hr
r--- - - Ta 1R'b"'f---T--t-- ::l
J J J
0
0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200
T. in K
Figure 11 Temperature dependence ofthe magnetic susceptibility of metals. (Courtesy ofC. J.
Kriessman.)
2. Humlmles. Apply the Hund rules to find the ground state (the basic level in the
notationofTable1)of(a) Eu++, in theconfiguration4[1 5S
2
p6;(b)Yb3+;(c)Tb
3
+.The
resultsfor(b)and(c) areinTable1, butyou shouldgivetheseparatestepsin appl yi ng
the rules.
3. Tripletexcited states. Someorganic molecules have atriplet(S = 1)excitedstateat
an energy kBil above a singlet (S = 0)ground state. (a) Find an expression for the
magnetic moment (J-L ) in a field B. (b) Show that the susceptibility for T p il is
approximately independent ofil. (c) With the help of a diagram of energy levels
versus field andaroughsketchofentropyversusfield,explain howthissystemmight
be cooled by adiabatic magnetization (not demagnetization).
438
4. Consider two-Ievelsystemwith
andIowerstates; thesplittingmay arisefrom
Show that the hoat capacity per system is
c
capacity
interaction between nuclear and electronic
electronspinorder)
'1'l'",L111!,' are often detected experi-
intheheatcapacityin the region T P .
interaetions (see with fields al50
spin of aconductioneleetrongas atabso-
another method.
betheeoneentrations eleetrons. Showthatinamagnetie
field B the total energy ofthe spin-up band in a free eleetron gas is
+(),
where in zero magnetic field. Finda
similar + E- withrespectto , andsolve
for the value of, in the approximation , 1. Go to show that the
in agreement with
6. approximate the eHeet of inter-
aetions among the eonduction electrons if assume that eleetrons with parallel
witheachother\vithenergy is positive, whileelectronswith
notinteractwitheachother. Showwiththe ofProblem5
(1 + () ;
find asimilarexpressionfor thetotalenergyand for in the
limit {, 1. Show that the magnetization is
so the interactionenhancesthesusceptibility. (c) ShowthatwithB = 0
thetotal energyis unstableat' 0 whenV > thisis satisfieda
neUc state({, "'" 0) will have alower energy than paramagnetic state. Because of
the assumption t: l, this is a sufficient condition for butit may
not be a neccssary condition. It is known
439
1
eNT" = 4.3 x
0.002 0.004 0006 0008 0.01
14 Dinmaf!:netism and Paramagnetism
0.5 r-j--,------r---,---,---,--i
Figure 12 Heat capacity of a two-level system as a function of T/t;,., where t;,. is the level splitting.
The Schottky anomaly is a very useful tool for determining energy level splittings of ions in rare-
earth and transition-group metals, compounds, and alloys.
0.008
0006
;.0
1
(3
E
0.004
E
.S
h
u
"
0.002
Figure 13 The normal-state heat capacity of gallium at T < 0.21 K. The nuclear quadrupole
(G T 2) and conduction electron (G 0: T) contributions dominate the heat capacity at very low ct:
temperatures. (After K Phillips.)
""
.l
~ 0.3
"
S

,J
p,
'"
8 0.2
0.1
00
Level2
1
,:;
j
Level l
4 5 6
x = Tlt.
TO, in K
J
u= c=
7. Two-levelsystem. TheresultofProblem4isoftenseeninanotherform. If thetwo
energy levels are at and -il, that the energy and heat capacity are
of are
proportionalto the tem-
to the heatcapacity ofdilute
1519 Itis al50 used in the
8. Itystem. Findthemagnetization
1,moment
as afunction
field andtemperaturefor asystemofspinswithS
n. (b) Show that in the limit li-B <{kT result is -
A. Abragam and B. Bleaney. Electron resonance tom, Dover, 1986.
B. G. Casimir, Magnetism andvery temperatures, DoveT, 1961. Ac1assic.
Darby and K. R. Taylor, Physics ofrare earth Halsted, 1972.
A. J. Freeman, The actinides: electronic structure and related properties, Academie, 1974.
R. D. Hudson. Principles and Elsevier, 1972.
North-Holland, 1970. Knoepfel, Pu/sed
Lounasmaa, and methods below 1 K, Academie Press, 1974.
Introduction ta transition metal 2nd ed., Wiley, 1966.
Van Vleck, The theory Oxford, 1932. deriva-
tions of basic theorems.
G. K. White, 3rd Oxford, 1987.
R. White, Quantumtheory
A. J. FreemanandG. H. Lander, actinides. North-
Holland, 1984-1993.
Sturge, "Jahn-Teller effect in solids," Solid state 91 (1967).
O'Brien and C. C. Chancey, "The effect: An introduction and current re-
view," Amer. J, Physics 61, (1993),