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Quantum Theory I

Jens Kortus
Jens.Kortus@physik.tu-freiberg.de
TU Bergakademie Freiberg

Some recommendations :
A.C. Phillips, Introduction to Quantum Mechanics
Sakurai & Napolitano, Modern Quantum Mechanics
Feynman, Lectures
Greiner, Quantum Mechanics: An Introduction
Konishi & Paffuti: Quantum Mechanics: A New Introduction
many more

Warning! This script may contain errors. Warning!


It is strongly recommended to check all derivations and
Formulas themselves.
.
Please send any corrections and comments to
Jens.Kortus@physik.tu-freiberg.de

Pictures: If not stated explicitly otherwise, the pictures are from


http://de.wikipedia.org/ or have been created by the author.
2

Motivation
Why do we need quantum mechanics:
stability of atoms (positive and negative charges)
System of elements
Chemical bonding, molecules
Solid state
spectroscopy (colors -> emission + absorption, laser)

Applications
NMR, ESR, Squids
medicine (nuclear spin tomography, laser-scalpel)
chemistry

Dreams (but in principle already doable)


Atomic construction (STM -> move single atoms)
Theoretical predictions of materials properties
Computer aided molecular design (pharmacy, dyes)

IBM Almaden STM Image Gallery

Xenon on nickel (110)

Iron on Copper (111)

Carbon Monoxide on Platinum


(111)

Kanji characters for


atom
http://www.almaden.ibm.com/vis/stm/atomo.html

1. Some experimental observations


1.1 Planck radiation law (black body radiation)
Thermal radiation (e.g. iron shows different colors with increasing temperature)
IR (heat) red yellow white
Interestingly, the colors depend only on temperature but not on the material.
Oven

Black body radiation: because there is no radiationat T = 0


Which frequencies and intensities will occur?

Rayleigh-Jeans law:
classical electrodynamics (dipole radiation) and statistics (equal partition)
At thermal equilibrium each degree of freedom contains an energy of kT/2.
Calculation of the energy of the electromagnetic field in the oven
Due to reflecting boundary conditions there will be standing electromagnetic waves
Each wave has energy kT (kT/2 electric, kT/2 magnetic) , k=Boltzmann constant
Need to count the number of such waves in a frequency interval [v + dv]

Cube with length a


standing electric waves have minima at the walls
standing magnetic waves have maxima at the walls
y
/2

x cos=n1 / 2
y cos =n 2 / 2
z cos =n 3 / 2
x

Standing waves are created, if they can fit


an integer number times there
wavelength/2 into the box.

n1 = 2a cos n2= 2a cos n3 = 2a cos


using cos2 +cos 2 +cos2 =1
n21 +n22 +n23 =(2 a )2 =(2 a c )2 =c
= 2ac (n21 +n22 +n23 )

Frequencies between 0 und v are within a sphere with radius 2av/c.


However, there are only positive integer n, so that in case of a>>,
the number of frequencies is equal to 1/8 of the volume of such sphere.

1 4 2a 3
N ( )=
(
)
8 3
c
2
d N ( )=4 a 3 3 d
c
spectral energy density d =2kT d N ( )T 2 d

Rayleigh-Jeans law: ~ T 2
2T

Radio

IR

light

UV

Roentgen

Only correct in case of small frequencies or large wave length (=c/)


-> UV catastrophe: intensity diverges for small ->
Classical physics is giving a wrong result here!

Wien law:
3

~ e

=h/ k

Only correct for large frequencies or small wave length


we need a mix of both radiations laws

Max Karl Ernst Ludwig Planck


* 23. April 1858 in Kiel
4. Oktober 1947 in Gttingen
Nobelpreis 1918

Planck radiation law (1900)

h
kT

e 1
h /kT

h
kT

large(e
1): e
x
small(e =1+ x+ ...):2 kT

Interpolation between Rayleigh-Jeans and Wien law.


Interpretation: Atoms behave like harmonic oscillators and can only have discrete
energies
E=hv (n+ ) = (n+)
The oscillators can only accept or emit energies equal to an integer n times a constant.
h = Planck quantum = 6.626 10-34 Js

=h/2

Light has wave length between 400-700nm.


This corresponds to energies of hv = 2 ... 4 eV.
Surface temperature of our sun is 5800K.
http://www.webgeo.de/beispiele/rahmen.php?string=1;k_304;1

1.2 Stability of atoms

Ernest Rutherford
1st Baron Rutherford of Nelson
August 30, 1871 October 19, 1937
Nobelpreis Chemie 1908

Scattering of -particles (He2+) at atoms in a gold foil.

Some -particles were scattered back to


the source. This means that there should
be heavy positively charged centers in the gold.

According to classical pictures electrons move around the core like planets around the sun.
However, movement along a circle is an accelerated motion.
According to classical electrodynamics: Any accelerated charge will emit EM-radiation,
which results in a loss of energy, so that the electron will fall into the core.
This would result in a radiation decay of atoms during a time span of about 10 -8 10-10 s.

10

1.3 Photoelectric effect


Metal plate in vacuum radiated with UV-light.
1) There is a minimal frequency for each metal below
no photo-electrons can be found.
2) Very fast process (<10-9s)
3) kinetic energy of the electrons for v>vmin
proportional to the frequency v of the light.
4) Number of electrons proportional to intensity.

Explanation by Einstein 1905

Albert Einstein
* 14.3. 1879 Ulm
18. 4. 1955 Princeton
Nobelpreis Physik 1921

Light = particles with energy E=hv (photon)


Each photon kicks an electron from the metal.
hv
corresponds to the binding energy of the electron in the
min
metal.
Electron number is proportional to the number of photons
(intensity).
Kinetic energy is proportional to h(v-v
)
min
11

Christiaan Huygens

1.4 Particle-wave dualism


a) Wave character of light
Interference and diffraction (Huygens 1678)

* 14. April 1629 in Den


Haag
8. Juli 1695

Double slit

Diffraction at single slit

Light is an electromagnetic field, fields can be superposed.


Er = E1 E2

The intensity is the energy density ~ |E|2.


Intensities can not be superposed. Picture is not sum of single pictures
2
2
2
2
I = ErEr =Er =E1 E2 E1 E2

b) Particle character of light


-> see photo-electric effect

12

Waves of matter: de Broglie 1924 (Dissertation)

Louis-Victor Pierre Raymond de


Broglie * 15. August 1892 in Dieppe,
Normandie
19. Mrz 1987 in Louveciennes
Nobelpreis Physik 1929

All particles (atoms, molecules, solids) can have wave properties.


The de Broglie wave length of moving particles with momentum p is
=

h
p

e.g. electrons with 10 keV kinetic energy have =0.12 (Rntgen radiation).

Waves: Amplitude and phase, direction, polarization, wave length easy to measure
matter-waves: direction in direction of momentum, de-Broglie Wellenlnge
Phase velocity can not be measured
Indivisibleness of particles: there will always be complete electrons in contrast
to light (reflected and diffracted ray).

Applications: electron microscopy, Neutron scattering


13
Quantum optics, Quantum communication, Quantum computer, Quantum teleportation ...

Double slit experiment with classical


particles

only 1 open

only 2 open

both open

Double slit experiment with


waves
How about electrons?

Bilder von David M. Harrison, Dept. of Physics, Univ. of Toronto


http://www.upscale.utoronto.ca/GeneralInterest/Harrison/DoubleSlit/DoubleSlit.html
http://www.upscale.utoronto.ca/GeneralInterest/Harrison/DoubleSlit/Flash/Histogram
.html

14

Wave character of electrons


1927 Electron diffraction using a Ni-crystal (Davisson & Germer)
1961 Double slit experiment with electrons
Claus Jnsson, Tbingen, Zeitschrift fr Physik 161, 454 (1961)

Electrons show particle or wave properties similar to light.


The Jnsson experiment has been selected in September 2002 by the journal 'Physics World' as the most beautiful
experiment of all times. http://physicsweb.org/articles/world/15/9/2

15

Wave-particle dualism for molecules: C60

16

"Wave-particle duality of C60" Markus Arndt et al., Nature 401, 680-682, 14.October 1999

2. Wave equation for free particles


2.1 Wavefunction
Based on the particle-wave duality we can describe the state of any physical system
with help of a wavefunction (r,t).
The square |(r,t)|2=* is the probability density to find a particle at location r
at time t.
The wavefunction (r,t) is a complex scalar, because there was no polarization found
In contrast to electromagnetic waves.
The probability to find the particle at time t in a volume element d 3r located at r
is given by
w(r,t) d3r =|(r,t)|2d3r=* d3r.
Probability density

w(r,t) =|(r,t)|2=*

A single particle has to be somewhere in a given volume, therefore:


w(r,t) d3r =|(r,t)|2d3r=* d3r=1
Normalization: If the above condition is not fulfilled for (r,t) then we can always
normalize to 1, by:
r , t 2
17
r ,t =

r ,t 2 d 3 r

Wavefunction (r,t)
Probabilities are positive definite numbers. Only the square has a real physical
interpretation. The wavefunction (also called probability amplitude) (r,t) itself
can not be measured and no real physical interpretation.
For many equal photons (bosons) the intensity is given by the square of the
wavefunction resulting from the superposition of the single photons
|(r,t)|2 = large -> many photons
|(r,t)|2=0 no photons

If there are alternative possibilities which will result in the same result then there
will be interference phenomena observed in QM. If the experimental setup is changed,
so that the alternate possibilities can not be realized, the interference will vanish too.
One possible interpretation of the wavefunction of matter is a statistical interpretation.
A single measurement will always detect a single particle, however the distribution in
space and time is given by the square of the wavefunction.
There is no certainty to find a particle at a given location and time, but only a probability.
18

Motivation Schrdingers equation

Goal: To find the equation which gives as solution the wavefunction for particles.
Schrdingers equation can not be derived directly from first principles.
Therefore we try to 'guess' Schrdingers equation based on the wave-particle duality
in analogy to light waves.
Wave-particle duality well proofed experimentally
All particles with constant momentum have a wavelength (de Broglie 1924)
QM as a general theory should contain the macroscopic correct classical mechanic in
certain limits (Hamilton-Jacobi theory)

19

2.2 Light waves (classical electrodynamics)


Wave equation from the Maxwell equations in case of the electric field:

E r

1 2
, t = 2 2 E r , t
c t

Ansatz: plane waves

r ,t = E0 e i kr t
E

will be a solution if =c k
Wave vector k points in the direction of motion.
e.g. k || x-Axis
E(x, t)=E0 cos(k x -t)
Period
: E(x,t+)=E(x,t) -> = 2
= 2/ = 2 v
Wavelength : E(x+,t)=E(x,t) -> k = 2
k = 2/
=c k -> 2 v = c 2/ -> v = c
Interference: E will be added (super position), because Maxwell eq. are
linear differential equations
Intensity: ~ Energy-current density (Poynting vector) ~ |Re E|2

22 =Re E12 Re E
22 2 Re E1Re E
2
Re E1 Re E
Intensity can not be superposed!

20

Remark on theory of special relativity


ED is a relativistic theory (c= speed of light), so that a relativistic wave equation
results into quantum electrodynamics.
E=mc2
E2 = m2c4 = p2 c2 + m02c4
Energy and mass increase with momentum (velocity).
Transition to classical mechanics in case of small p (c>>|v|)

E= m c p c =m0 c
2
0

p 2 c2
1 p 2 c 2
1 p 2
2
2
1 2 4 ~m0 c 1
=m0 c
2 m20 c 4
2 m0
m0 c

1 x~1 12 x ...

Light m0=0 photons have no rest mass but momentum


-> E2 = p2 c2 E = |p|c

p=|p|

E = hv = = c k = p c
E =
p = k

-> p= k

( p = k )

Energy photon
momentum photon

because k=|k|=2/

p= k = 2/ = h /

Therefore any particle with fixed


momentum has a well defined
wave length.

de Broglie 1924

21

2.3 Relativistic equation matter waves (Klein-Gordon equation)


Similar to light we are searching for an equation where the solution for free particles
will be a wavefunction (r,t) given by a plane wave

r ,t = 0 e i kr t
Due to the experimental known wave-particle duality we additionally require the
Energy and momentum relations from de Broglie:
E =
p = k

energy
momentum

Using the relativistic equation now with m00: E2 = m2c4 = p2 c2 + m02c4, we obtain:

2 2 = 2 c 2 k 2 m 20 c 4
2
2
2 2
2 4

= c m0 c
2
t
Klein-Gordon equation 1926

=i
t

=i k j
xj

(only correct for spin less particles - bosons)


2

2
1 m0 c
2
= 2
c t2

22

2.4 Non-relativistic equation for matter (Schrdinger 1926)


We start from classical mechanic and require energy and momentum relations for light
due to the wave-particle duality.

r ,t = 0 e i kr t
Classical kinetic energy E = p2/2m, E = , p = k
2

2m
2
i
=

t
2m
=

=i
t

=i k j
xj

In case of a particle in external potential U(r) one can generalize this using the classical
Hamilton-function H = p2/2m + U(r), which corresponds to the total energy of the system.
2

r ,t
i
=

r ,t U
r
r ,t
t
2m
Schrdinger equation
Erwin Rudolf Josef Alexander Schrdinger
* 12. August 1887 in Wien-Erdberg
4. Januar 1961 in Wien
Nobelpreis Physik 1933

23

2.5 Wave packets and coherence length


A Gauss wave packet is a wave modulated by a Gauss-function (Multiplication of the wavefunction by a Gauss-function).

Coherence length = Length of the wave


In reality wave have mo infinite extension like plane waves, but are rather given by
Wave packets. Interference will only occur if the coherence length l c is large
compared to the dimension of the measurement apparatus.
e.g. realistic life times for radiation of a photon from an atom are about ~10-8s.
This corresponds to a coherence length lc=c* ~ 3m of the wave packet.

24

3. Wavefunction, Schrdinger equation and operators


The state of a QM system will be described by its wavefunction
(r,t)=wavefunction=state function
Probability density to find an electron at location r and time t is defined by the square
of wavefunktion.

(r , t )2
* (
r , t ) (
r ,t)
w(r , t )=
=
(r , t )2 d 3 r * (r , t ) (r ,t )d3 r
The wavefunction is the solution of the Schrdinger equation.

r ,t

i
= H =

r , t U r r ,t
t
2m
H = Hamilton-operator
(Operator: Function -> Function)
Build from the Hamilton-function as defined in classical mechanics.
25

Example: free particle in large volume V


free = no acting forces -> potential energy U(r)=0
Schrdinger equation:

r ,t
2
i
=H =

r ,t
t
2m
Solution will be plane waves:

(r , t )=0 e

i(
k
r t )

with

(
k )2
=
2m
2 2

2
k
2
i i =
k

2m
2m
Normalization of the wavefunction

* d3 r= 0* ei kr t 0 e i kr t d3 r = *0 0 d3 r= 0* 0 d3 r = *0 0 V =1
1
V
We get a plane wave with fixed energy E = and momentum p = k
wave vector k || p and group velocity
0=

v g k =

d
dk

k
=v
m

Where do we find the particle?


|(r,t)|2 = 1/V
The probability is equal in all points of space.

26

3.1 Operators and measurements


Momentum operator: classical momentum p will be replaced by QM operator pop

,
,
= grad=
i x y z
i
i

2
2
2
2
2
2
2

pop = poppop = = = =

i
i
x 2 y 2 z2
pop =

Position (space) operator: classical position r will be replaced by QM position operator rop
r -> rop = just multiplication with value r
Function depending on coordinates U(r) -> Uop(r) multiplication with value of function
Index op will not be used further!
The order of operators can not be permuted in the general case!


r ,t
i
x

r , t
p x x r , t = p x x
r , t =
x
r , t = r , t x
i x
i
x

x p x p x x
r , t =
r , t
i
x p x r , t = x p x
r , t = x

27

Eigenvalues of operators correspond to physical values of measurements.


Eigenvalue equation from linear algebra

a 11
a 21

a 12 x 1
= x 1
a 22 x 2
x2

A x= x

QM: Operator function = Number function


A) momentum measurement for plane waves:

pop = grad = p
i

r ,t = 0 e i kr t

p =
k nach de Broglie

B) Hamilton operator free particle

p2op
2
H op =
=
2m
2m
2
pop
2 k2
H op =
=
=E
2m
2m
Eigenvalues of the Hamilton operator are just possible values of the energy.
C) general case: Operator A corresponds to a certain physical measurement

Eigenvalue equation A =a
Eigenvalue a=possible value of measurement

28

3.2 Formal quantization


In the classical Hamilton function H=p2/2m+U(r) all classical values like space and
momentum are replaced by there corresponding QM operators

,
,
= grad =
i x y z
i
i

E i
t

As a results we obtain a linear partial differential equation for the wavefunction (r,t).


r ,t
=H
t

Schrdinger equation

Linerar equation: if (r,t) will be a solution, then also constant*(r,t) will be a solution:
Therefore normalization needed: |(r,t)|2d3r=* d3r=1

Remark: The choice of classical generalized coordinates may in some cases not unique.
The order of mixed position and momentum coordinates does not matter in classical
mechanics, which is not true in QM. The freedom of choice vanishes if we use always
Cartesian coordinates together with an additional replacement rule: p q -> (qp+pq)/2
29

3.3 Stationary (time independent) states


In case of an Hamilton operator which does not depend on time, it is possible to derive
from the full time-dependent Schrdinger equation a stationary Schrdinger equation.

2
(r , t )

i
=H =
(
r ,t )+ U (r ) (
r , t)
t
2m

( r , t )=f (t )(
r)

Ansatz: Separation of variables

i (
r)

f (t )
=H f (t ) (r )
t

Dividing by (r,t) one obtains the stationary Schrdinger equation H (r) = E (r).
The solution (r) are called stationary states which have fixed energy.
The time part equals to f(t)=e-it with E = .
*

w(
r , t )= (
r , t ) (
r , t )=e

it

( r )e

i t

( r )= (
r )(
r )=w(
r)

The probability density is time independent, even if the wavefunction is still


time dependent (r,t) = e-it (r)
30

3.4 probability current


*

*
*
=

t
t
t
Schrdinger equation and the complex conjugated one
2

r ,t

r , t
*
i
=

r ,t
i
=
r ,t
t
2m
t
2m

*
=
* * ]

[
t
i 2m
Definition of the probability current density:

=grad

j r ,t = [ *
r , t r , t
r , t *
r , t ]
i 2m
This allows to formulate a continuity equation

w
r ,t div j
r , t =0
t
The change in time of the probability w(r,t) in a given volume equals to the
probability current through the surface of the volume.
(similar to charge conservation in ED, or mass conservation in continuum mechanics)
31

4. Some very basics of probability calculus


Result of a single experiment can not be predicted in the general case.
However,it is possible to make statistical predictions for many experiments.
Def.:
Physical property :
A
(energy, momentum, ...)
Measurement value of A: a
(possible values from measuring A)
probability w(a), to measure the value a

N (a)
N N
N =number of measurements
N (a)=number of mesurements with result a
0w (a)1
w(a)=1
w(a)= lim

Physical properties are often continuous (e.g. space) and not discrete.
w(a) becomes a probability density
w(a)da= probability to find the value a within the interval [a-da/2,a+da/2]

w a w a da
32

4.1 Averages (expectation values)


Average of the property A is also called expectation value

A =
A = a w a
a

Average of a function f(A)

f A= f a w a
a

f A = f a w a da
a

Which experiment is more accurate?


2,5

2,3
2,2
2,1
2
1,9
1,8
1,7
1,6
1,5
1,4

2
1,5
1
0,5
0
0

6
Messungen

10

12

6
Messungen

10

12

33

Average of the distance from the expectation value is not good:

A A = A A =0
4.2 average quadratic deviation = uncertainty

A= A A
2

A = A 22 A A A 2 = A 2 2 A A A 2= A2 A 2
A= A2 A 2
Most physical properties have A0.
-> measurements of the same property deliver different results
(Heisenberg uncertainty principle: xp/2)
There are cases, e.g. stationary cases, where the uncertainty may vanish (A=0).

The aim of QM is often to calculate the possible eigenvalues (measurement


values) a of a physical property A together with their probabilities w(a).
34

5. Simple Examples
5.1 Particle in 1D-box with infinite walls
U

U=0
=
0

for 0 x L
outside
2

1D Schrdinger eq.:

x , t
x , t
i
= H x , t =
U x x , t
t
2m
x2

We search for stationary states (solutions for fixed energy) H=E.


2

x
U x x =E x
2m x2
Finite energies are only possible if (x)=0 outside the box.
Boundary conditions for the solution of Schrdinger equation between 0 x L
will be (0)=(L)=0.
There exist an infinite number of solutions n fulfilling the boundary condition
with different energies En.
2

2 n x
= En x
2
2m
x

n x = a n sin k n x
n x = b n cos k n x

35

The boundary conditions select from the general solution compatible ones
(0)=0 -> all bn=0, because cos(0)=1
(L)=0 -> knL= n, because sin(n)=0
-> kn= n/L

n x =an sin


n
x
L

n=1, 2, 3, 4, ...

an from normalization
L

2
L

1= *n n dx = a2n sin 2
0

a n=

n
2n
2n
L
1
1
L
x dx =a2n 1cos
x dx =a2n x
sin
x =a2n
L
2
2n
2
L
L
0 2
0
2

cos 2 =cos sin =12sin


1
2
sin = 1cos2
2

x/L

x/L

36

Energies can be obtained from putting n(x) in the Schrdinger equation:


2

2
2
2
n x n
n
E n x =
=
a
sin
x
n
2
2m
2m L
L
x
2
2
2 k 2n
n
E n=
=
2m L
2m

Due to the boundary condition not all energies are allowed anymore.
The discrete energy levels correspond to the measurable energy eigenvalues of
the system. This is a qualitatively new results of QM.
The uncertainty of the energy is the state n vanishes En=0.

A n=an n
A2 n = A A n = A a n =a 2n n
Distance between two energy levels
2



2
2
E n1 E n =

n1
n

=
2n1
2m L2
2m L 2

L large: very small energy differences, practical energies appear continuous


L small: only discrete energy differences allowed (-> sharp spectral lines)

37

Absorptions spectra of aromatic ring molecules


2



2
2
E n1 E n =

n1
n

=
2n1
2m L 2
2m L 2

E = hv = = c k = h
c /
Absorption spectra of aromatic molecules
Show with increasing molecular size a
shift to larger wave length
(smaller energies).
Electrons in -bonds are only weakly bonded
and can be approximately described by
particles in a box of a length given by the
size of the molecule.

Haken&Wolf, Moleklphysik und Quantenchemie, S.259

38

5.2 Particle in 3D-box with infinite walls

2 2
2
2

2 x , y , z = E x , y , z
2
2
2m x
y
z

L3
L1

L2

Similar boundary condition as before:


0, y , z = L1, y , z = 0
x ,0 , z = x , L 2, z =0
x , y ,0 = x , y , L3 =0

Ansatz: Separation of variables (x,y,z)= (x) (y) (z)

n n n x , y , z =
1

n
2
sin 1 x
L1
L1

n
2
sin 2 y
L2
L2

n
2
sin 3 z
L3
L3

2
2
2
2 2 n 1 n2 n3
En n n =

2 2
2
2m
L1 L 2 L 3
1

Sommerfeld model of metals: explanation of electric conductivity using QM

39

5.3 Tunnel effect


classical Mechanic
Reflexion, Scattering

U0

kinetic energy smaller than U0

U0

kinetic energy larger than U0

QM: What are the states with fixed energy?


I

II
0

(general solution for 2. order differential eq.


-> see Mathematics)

III
L

2 d 2
I:
x =E 1 x
2m dx 2 1
2 d 2
II:
x U 0 2 x = E 2 x
2m dx 2 2
2
d2
III:
x =E 3 x
2m dx 2 3

1 x = A 1 e

ik1 x

i k 1 x

B1 e

2 x = A2 e

i k2 x

B2 e

i k 2 x

3 x = A3 ei k x B 3 ei k
3

2 2
E=
k
2m 1
2 2
E=
k U 0
2m 2
2
2
E=
k
2m 3

Energy given and constant in all parts (energy conservation)


k 1 =k 3 =

1
2m E

k 2=

1
2m E U 0

k2 for E<U0 imaginary k2=i

40

5.3 Tunnel effect


classical Mechanic
Reflexion, Scattering

U0

kinetic energy smaller than U0

U0

kinetic energy larger than U0

QM: What are the states with fixed energy?


I

II
0

(general solution for 2. order differential eq.


-> see Mathematics)

III
L

2 d 2
I:
x =E 1 x
2m dx 2 1
2 d 2
II:
x U 0 2 x = E 2 x
2m dx 2 2
2
d2
III:
x =E 3 x
2m dx 2 3

1 x = A 1 e

ik1 x

i k 1 x

B1 e

2 x = A2 e

i k2 x

B2 e

i k 2 x

3 x = A3 ei k x B 3 ei k
3

2 2
E=
k
2m 1
2 2
E=
k U 0
2m 2
2
2
E=
k
2m 3

Energy given and constant in all parts (energy conservation)


k 1 =k 3 =

1
2m E

k 2=

1
2m E U 0

k2 for E<U0 imaginary k2=i

41

Boundary condition: wavefunction should be continuous


d
d
1 0 =
0
dx
dx 2
d
d
2 L =
L
dx
dx 3

1 0 = 2 0
2 L = 3 L

II
0

III
L

4 equations but 6 unknowns, one additional condition due to normalization


-> one of the unknowns is not determined -> use experimental setup to define one
e.g. particles come only from part I but not from III B 3=0 (no back scattering in III)
I

II

III
A3 corresponds to classical forbidden contribution

Using the conditions together with the general solution we obtain a linear system of
equations to solve for the unknown constants.

A2 e i k

A1 B1 = A 2 B 2
L
i k L
ik
B2 e
= A3 e
2

A1 k 1 B 1 k 1= A2 k 2 B 2 k 2
A 2 k 2 e i k L B 2 k 2 e i k L = A 3 k 1 e i k
2

42

a) E> U0 k1, k2 real numbers solution have wave character

b) E<U0 (classical reflexion)


2

A3
admission coefficient D=
A1

B1
reflexion coefficient R=
A1

Particle should not vanish in the barrier (II), therefore D+ R = 1.


A3
4 k 1 k 2 ei k L
=
A 1 k 1k 22 eik L k 1 k 2 2 eik

A3
4 k 21 2
D=
= 2
2 2
2
2 2
A1
k 1 sinh L4 k 1

43

k 1 =k 3 =

1
2m E

sinh L=
2

1
2m U 0 E

1 L L 1 L
e e e
2
2
2

falls L1

1
sinh 2 L e 2 L
4
2

A3
4 k 1
16 k 1 2 L
D=
= 2

e
2 2
2
2 2
2
2 2
A1
k 1 sinh L4 k 1
k 1

Typical for solids (metals) U0-E~5eV,


In case of electron :
L=1 : e-2L ~ 0.1
L=2 : e-2L ~ 0.01
L=10 : e-2L ~ 10-10
The admission decreases exponentially
with the width L of the barrier.
The bigger the mass the smaller is the
admission coefficient D.

44

Is the tunnel effect important?


Qualitative understanding of the chemical bond
Due to the tunneling process the total energy of the system can be lowered
-> this is one reason for binding energies
benzen: Collective tunneling of all double bonds -> all C-C bonds have the same length

Radioactive -decay

1/r

-particles are able to tunnel out of the nuclear box

45

6. Hilbert space and linear operators (mathematical foundation QM)


6.1 Hilbert space
space = mathematical construct: vector space
a) The linear complex space is the set of mathematical objects having the following
properties
1. and are elements of the set, then is also an element of the set.
2. It exist one element 0 (zero element) with +0=, -=0.
3. If is an element of the set, the is (= complex number) also element of the set.

David Hilbert
* 23. Januar 1862
Knigsberg
14. Februar 1943
Gttingen

46

Examples:
I. Set of complex 3D vectors a=(ax,ay,az) with ax=Re ax + i Im ax
a, b are vectors, then is ab=(axbx,ayby,azbz) also a vector
a + (0,0,0)=a zero vector (0,0,0)
a=(ax,ay,az) is a vector ax = Multiplication of two complex numbers
II. Set of all wavefunction (state functions) which are solution of Schrdinger equation
(r,t) and (r,t) are solutions of Schrdinger equation, then is also a solution
function identical zero is solution of Schrdinger equation
(r,t) is also a solution
III. other mathematical sets (e.g. matrices)

47

b) Hilbert space of physicists


The Hilbert space is a linear complex space, which has defined additionally a scalar
product with the following properties:
0. (,) = a
= complex number (Mathematics: a is finite)
1. (, ) = (,)
= complex number
2. (,) = (,)* = a*
=> (,) = (,)* = [(,)]* = *(,)* = *(,)
(,12) = (,1) (,2)
=> (12,) = (1,) (2,)

(,) 0 and real, finite


(,) = 0 only if = 0

Def. Norm (length):

, are orthonormal, if

, =

0
1 =

, =

48

c) Hilbert space (mathematicians)


Additional requirement of completeness
Very important for mathematicians but any complex vector space can be completed

e.g., Completing rationale numbers by irrational numbers


limits have to be elements of the space
e.g. set of all real polynomials of order N,
form a linear space, scalar product defined as

f N x = a n x n
n=0

then

,f

f nf m dx
0

sin = limit of the polynomials


for N ->

x3 x 5
sin x=x = a n x n
! 5!
n=0Hilbert space:
Mathematical correct 3definition
of the
A linear complex space which is complete with respect to the metric induced by the
scalar product, this means that all Cauchy series will converge, is called Hilbert space.

49

Basis in Hilbert space


There are sets of elements of the Hilbert space, i=1, 2,..., which are orthonormal
i , j = ij

and complete. The completeness means that any element of the Hilbert space can be
represented by a linear combination of the basis.
= a i i
i

All further properties can be derived from the definition of the scalar product.
e.g. the coefficients ai of the linear combination are given by:

i , = i , a j j = i , a j j = a j i , j = a j ij =a i
j

50

Examples
complex vectors

*
*
*

a ,
b=a x b x a y b ya z b z

a= a x2 a y2 a z2

real vector

The solutions of Schrdingers equation (wavefunctions)


are elements of a Hilbert space with a scalar product defined as:

, = = * r ,t r , t d 3 r
Paul Adrien Maurice Dirac
* 8. August 1902 Bristol
20. Oktober 1984
Tallahassee
Nobelpreis Physik 1933

, = d r = d
r = ,
*

, = d r = d r
, = * d 3 r = * * d 3 r = * * d 3 r
*

, 1 2 = 1 2 d r = 1 d
r 2 d r = , 1 , 2

Dirac notation for the scalar product <|>


bra = <|
ket=|>

51

Comparison N-dimensional vektor space with Hilbert space

Vector space
a
{en}
eiej=ij
a = ai ei
ai = eia
ab = ba

Vector
Basis
Orthogonality
linear combination
Symmetry scalar product

Hilbert space

{ n}
< i | j> = ij
= a i i
a i = <i | >
< | > = < | >*

The elements of the Hilbert space in QM are normalizable functions, the dimension of
Hilbert space is infinite. The basis is given by a suitable, complete and orthonormal set
of functions.

52

6.2. Mathematical properties


1. Schwarz inequality
,= , ,
(real vectors

a= a a a
2
x

2
y

= length of vector)

2
z

a
b=abcos ab

cos 1

2. triangle inequality


real vectors
= Length a

a
b

53

6.2. Mathematical properties


1. Schwarz inequality
,= , ,
(real vectors

a= a a a
2
x

2
y

= length of vector)

2
z

a
b=abcos ab

cos 1

2. triangle inequality


real vectors
= Length a

a
b

54

6.3. Linear operators in Hilbert space


Def: An operator maps an element of the Hilbert space on another element.

A =
Matrix in the space of 3D vectors

a xx
a yx
a zx

a xy
a yy
a zy

a xz b x
cx
a yz b y = c y
a zz b z
cz

x 1, y 2, z 3
3

aij b j=ci

Einstein:

a ij b j =ci Summation over


double index
(Einstein
sum convention)

j=1

=
x
Translation operator

T x , y , z = xa , yb , zc
Operator must not known explicit, knowing its result is sufficient!

Inversion operator

P r = r
55

Def: Operator A is linear if:

A 1 1 2 2 =1 A 1 2 A 2
Example for nonlinear operator:

Multiplication with

A = ,
A = ,
In general

e.g. A = px, B = x

AB B A
Def: The combination of two operators A and B in the following way:
AB BA =[A,B] = C (another operator) is called Commutator.

[ x , p x ]=i
[ x , p y ]=0
[ x , x ]=0
[ p x , p x ]=0
56

Def: Inverse operator (undo operator)


B is inverse to A if AB = BA = 1.
B = A-1
(only notation not 1/A , px-1 -> integration)
AA-1 = 1
e.g.

1 = integration

x
x
Def: Adjoint operator
B is called adjoint operator to A if

, A = B ,= A ,

B= A*

1 A1 2 A2 * = *1 A*1 *2 A*2
AB* =B * A*

, A B = A , B = B A ,
*

, AB= AB ,
AB* =B * A*
A** = A
Home work
57

Def: self-adjoint (hermitian) Operator


Operator A is called self-adjoint if A* = A.
All physical meaningful operators are hermitian (self-adjoint).
Def: Unitary Operator
Def: Operator U is called unitary if
U* = U-1
UU* = U*U = 1
The scalar product is invariant under any unitary transformation.
(U,U) = (,)

(U*U,) = (,)

Example: Translation operator T(x) = (x+a)


location x shifted by constant a

, = dx x x

T , T = dx xa xa

= dy * y y

y= x a
dy = dx
58

Fourier-transformation
F[(x)] = (k)
(F,F) = (,)

Norm does not change

Examples for hermitian operators:


1)
, x = d 3
r *
r x
r
= d 3 r x r * r

position operator x is hermitian Operator (y, z similar)


= x operator
,
-> r is hermitian
partial integration

2)
p x = ,

dx f x dxd g x=

= d 3 r * r r =
i x
i x

= dy dz * x , y , z x , y , z xx =
=

*
d 3 r

r
r
i x

= f x g x dx

d
f x g x
dx

0, in case * and/or vanish at



= d r

r r =
, = p x
i x
i x
3

59

px =


i x

p =

Is a hermitian operator (py,pz similar)

grad
i

is hermitian operator

Remark
, are plane waves, e. g.
0 for

r =e

i k1
r

r =e

i k2
r


3
i k r
i k r
= d r e
e
i x
i x
1

= d 3 r ei k r
x

= k 2

d 3 r

x i k r
ik e
i 2

i k1 k2 r

= k 2x 2 3 3 k1 k2
60


, = d 3
r
i x


i k r
e
i x
1

= d 3
r k 1x e

= k 1 d r e
x

i k1
r

i k1r

i k2
r

i k2
r

i k2r

= k 1 d r e
x

i k1 k2 r

= k 2x 2 3 3 k1 k2

'

k k =
3

0 for
0 for

, px = p x ,

k1 k2
k1= k2
px is hermitian

Similar proof for py and pz, therefore if all components of the momentum operator
are hermitian then
-> p is hermitian
61

6.4 Eigenvalues and expectation values of hermitian operators


Measurement values are represented by hermitian operators.
The solution of the eigenvalue equation for operator A gives eigenvalues a n
and eigenvectors n.
A n=a n n
In case of an hermitian (self-adjoint) operator A the relation (,A)=(A,) is true.
n A n = na n n =a n n n

*
n

A n n = a n n n =a n n

a n =a *n

The eigenvalues of hermitian operators are always real numbers.

Charles Hermite
* 24. Dezember 1822 Dieuze (Lothringen)
14. Januar 1901 Paris

62
http://turnbull.mcs.st-and.ac.uk/history/PictDisplay/Hermite.html

The eigenvectors of hermitian operators form a basis in Hilbert space.


m A n = ma n n =a n m n
A m n =a m m n =a *m m n =a m m n
The difference of both equations in case of hermitian operators gives:

0=a n a m m n
Therefore, in case of different eigenvalues anam, the corresponding eigenfunctions
have to be orthogonal (scalar product is zero).
If one eigenvalue has several eigenfunctions (degeneracy), it is always possible
to build linear combinations of these eigenfunctions which are orthogonal
(Gram-Schmidtsch orthogonalisation).
By means of normalization of the eigenfunctions we obtain an orthonormal basis in
Hilbert space, so that any state can be expressed as a linear combination in that basis.

63

6.5 Expectation values of hermitian operators


Assume we know for an hermitian operator A the eigenvalues and eigenfunctions.
A n =a n n

Then we can represent any state of a physical system by a linear combination using the
basis given by the eigenfunctions of A.
= ci i = ci i
i

The expectation value to measure the physical property A in such state will be:

A = , A = A = A ci i = c i A i = c i a i i = c i a i i =
i

= a i c i c j j i = c j a i c i j i = c j a i c i ij = a i c i
i

c i = a i c i2
i

That means we will measure the value ai with probability |ci|2.


64

6.6 Hermitian operators and measurement


All physical properties can be represented by an hermitian (self-adjoint) operator.
The eigenvalues of such operators are always real numbers and correspond to the
possible measurement values of the physical property.
The eigenfunctions of any hermitian operator can be used as basis in the Hilbert
space, so that any state can be expressed as linear combination of these basis states.
The measurement of a physical property in a state delivers always an eigenvalue
with probability |ci|2. The probability is given by the contribution of the corresponding
basis function to the state .
If the system under investigation is already in an eigenstate, then we will always
measure the same eigenvalue corresponding to the eigenstate without uncertainty.

65

7. Heisenberg uncertainty principle


A*=A, B*=B are 2 hermitian linear operators (= physical properties)
1)

1
1
A , B A , B * = A , B B , A
2
2
1
= , AB , B A
2
1
= ,[ A , B ]
Because for any complex
number z holds:
2
A , B

z=
Im z
2)
Schwarz
Re z inequality
2

1
1
zz * = 2 i Im z = Im z
2
2

Square of the equation


,
= ,
, are arbitrary vectors, so that we replace these by new ones
, , , 2
Using the hermitian properties and 1) we obtain

A , B

A , A B , B A , B 2

, A2 , B 2

1
,[ A , B ] 2
4

66

A, B are also arbitrary operators, which we replace by new ones

A A A ,

B B B
2

1
2
,[ A A , B B]
4
Uncertainty of the measurement A in state ,
if the state is not normalized.
If normalized then (, )=1.
2

, A A , B B
2

, A A
A =
,
2

, A2 , B2

1
,[ A , B ] 2
4

[ Anumber , Bnumber ] = [ A , B ] [ A , number ] [number , B ] + [number , number ]

1 ,[ A , B ]
A B
4
,
1
[ A , B ]2
4
2

A B

1
[ A , B ]
2

Heisenberg uncertainty relation


67

Heisenberg uncertainty principle


The uncertainty is a measure for the deviation of the measurement values
from their average.
The Heisenberg uncertainty relation gives a lower limit for the product of the
uncertainty of physical properties. The lower limit is determined by the commutator
of the corresponding operators.

A B

1
[ A , B ]
2

The uncertainty relation describes the quantum mechanical uncertainty of the


measurement process itself. Only if the two operators commute [A,B]=0, it will be
possible to measure the physical properties at the simultaneously without uncertainty.

68

1
z.B. [ x , p x ] = i
A B [ A , B ]
2

x p x
2
All operators A, B, which commute

y p y
[A, B] = 0 ,
2
will give reproducible values

z p z
2 bigger (or if equal), depends on the specific state ()
how much

e.g.plane waves: have sharp momentum: px = 0


-> x =
Location is completely undetermined.
Slit
y
y

y finite -> py finite

py = 0
y =

Are exact determined locations with x = 0 possible?


-> px = not possible no

69

px

Harmonic Oscillator:

x
x
U
E

k 2
x
2
2
px
U
2m

Classical mechanic allows any elliptical curve.


Origin x = px = 0 corresponds to rest position.

U = 0 and px = 0 is not possible in QM, because then would be x = px = 0.


Therefore, it must exist a minimal energy, corresponding to zero point motion.
px
x

E min =

k
m

Remark: E.t /2 can not be derived, because t is not an operator.


Theory of relativity -> (px,py,pz,E/c) (x,y,z,ct) -> E.t /2
t = life time of a state
I
Uncertainty of the spectral line
seen as broadening.
+
E

70

8. Linear harmonic oscillator (1D)


classical:

k
= 2 f
m

(frequency)

k = 2 m

2 m 2
k 2
-> the
smaller
(deuterated
U =
x = truexfor all oscillationmaslarger
Approximately
long as
amplitude
is small molecules)
enough.
2
2
U

H
z.B.

H can move in x-, y-, z-direction

All 12 atoms: 3*12 degrees of freedom


3 translation + 3 rotation
-> 36 6 = 30 possible vibrations
(30 coupled linear harmonic oscillators)

71

Quantum mechanic:
We search stationary states using the stationary Schrdinger equation.

H n x = E n n
2 d 2
m 2 2
H n=

x n= E n n
2m dx 2 n
2

substitution =

0 = a 0 e

m / x

n x = n

2
2

2
2

1 = a1 e

2
2
n
n = e
[a 0 a 1 a 2 ...a n ]
2

a j2

2 jn
=
a
j1 j2 j

n ( x) e

m 2
x
2

Hermite Polynomial Hn(y)


Hn

( )

H n x

d y
= 1 e
ne
dy
n

1
Energy eigenvalues E n = (n+ )
2

72

Another way to find a solution:


Instead of the solution of the differential equation we replace the problem by
another one, which requires only the solution of algebraic equations
We define two new operator A and A+, in order to rewrite the Hamilton operator.

A =

m
x
2

Annihilation operator

ip x

Creation operator

2 m

ip x
m
x
2
2 m
A is not measurable, because A A+ (not hermitian)
from [x, px] = i , [x, x] = [px, px] = 0 we can calculate
A* = A =

[ ] [

] [

][

ip
i p x
ip
m
m
m i p x
m
x,
x x
,

x,
x
,
x
2
2
2

i
i
i
i
= [ x , p x ] [ p x , x]= [ x , p x ]= i =1
2
2

[ A , A+ ] =

73

Now we rewrite the Hamilton operator with help of A and A+


2

px
m 2 2
H =

x
2m
2

2 1
+
x=
A A
m 2
i
p x = 2 m
A A +
2

2
2
+
+
+2
x =
A AA A A A
2m
1
p 2x = m A 2 AA + A +A A +2
2

A =

A =

Inserting in Hamilton operator and using the previous result

m
x
2

m
x
2

ip x

2 m
ip x

2 m

[ A , A +]= A A+ A+ A=1

2
+
+
+2
2
+
+
+2
+
+
A AA A A A
A AA A A A =
2 AA A A
4
4
4

1
=
2 A +A1= A+ A
2
2

H =

74

This transforms the problem to the solution of the eigenvalue problem of


a new operator.
N = A +A

N is hermitian

occupation operator

N+ = (A+A)+ = A+ (A+)+ = A+A = N

-> real eigenvalues

N n = nn
n

Should be a normalized eigenstate

= n

AA + A+ A = 1

= A n
N = A + A A +n = A + 1 A + A n = A + 1 N n =n1 A+n = n1

therefore A+|n> = is eigenstate of N with eigenvalue (n+1)

_ = A n
+

N _= A A An = AA 1 An = AA A A n = AN A n =
= A N 1n =n1 A n = n1 _

75

In the same way one can show that An is eigenstate of N with eigenvalue n-1.
Using A+ one can climb up from n by 1 to the eigenvalue n+1, using A climb down by 1.
Going up is no problem in contrast to going down, because
+

nNn = nA An = A n A n
+

, N n = n , A A n = A n , A n 0
No neigenvalue
of N are allowed to be negative!
-> There exist a state
, which will vanish operating on A0 = 0.
0must different from 0
zero
=(||
0|| = 1).
0

In state 0 the operator N has the smallest eigenvalue n = 0.

1
1
H = A + A = N
2
2
The vibration of a harmonic oscillator in state |n> contains n vibrational quanta (vibrons),
which all have the energy . The Hamilton operator H describes a system of such
Vibrational quanta of equal energy (), where only the number of vibrons n can change.
The operator N just counts the number of vibrational quanta in the state |n> (occupation).
Application of A+ (A) on state |n> creates (annihilates) a vibron.
76

Ground state wavefunction 0(x) = wavefunction of state |0>


A 0 x = A 0 = 0

d
x
0 x = 0
2
2m dx

0 x = c0 e

m 2
x
2

m
d
0 x = c0
x
dx

m
=
2m

m 2
x
2

m
x

1 =

dx

*0 x 0 x = c 0 2

q =

m
2

Normalization

dx

m 2
x

m
x

= c0

dq =

dq

m
dx

q 2

c0 =

77

remaining eigenfunctions created by repeatedly operating with A +


1 =

1
4

m
1
d

0 =
d

1
d

d
2

2
2

n =

n! 2

Hermite Polynomial

Hn = e
n =

x2
2

d
x
dx

1
n ! 2n

1
4

x2
2

= 1
2
2

H n

d n x
e
e
dx n
x2

n = 0, 1, 2, . . .

78

Now, we know eigenvalues, eigenvectors of N = A+A


1 = A+ 0

1
+ n
n =
A 0
n !

En

A +n =

n1 n1

An =

n n1

discrete, non degenerate with


equal energy distance
n = 0, 1, 2, positive integer

1
= n
2

2
Zero point energy
E0 =

1
E0 =
2

Not allowed in QM!

x px =

2
79

The eigenfunction n has exactly n zeros.

IR-absorption between states of different parity (dipole selection rules)


~ nx m =

*n x m dx

Integral with symmetric limits of an


odd function vanishes.

n=0 -> n=1 strong transition


n=0 -> n=2 forbidden (equal parity)
80

Importance of the harmonic oscillators for physics


Any system which can vibrate (molecules, solids) is approximately a system of
coupled harmonic oscillators A transformation to so called normal coordinates
changes it into a system of uncoupled 1D harmonic oscillators.
Zero point energies are real and contribute to stability (lowering of binding energies),
and therefore also to the total energy and enthalpy.
13

C is in higher abundance in biological systems compared to inorganic processes.

Confirmation of Planck explanation of black body radiation.


Quantum electrodynamics is formulated usually in terms of creation and annihilation
operators, which means is based on the physics of the harmonic oscillator.

81

9.Two level systems


9.1 Ammonia (NH3)
H-atoms form an equal lateral triangle. The energetic favorable location of N is not
in the plane of the H-atoms, but above or below at the same distance and same energy.
Ammonia has obviously many different states, however we reduce it to a model with
only two states corresponding to the position of the N atom.

Dipole moment d

82

Lets |1> the normalized state with N above the plane of H-atoms and |2>
the mirrored one. The energy in both of these states will be equal.
1 H 1 = 2 H 2 = E 0

However, the states are different and should not overlap, so that <1|2>=0.
We can use these two states as basis states in a 2 dimensional Hilbert space.
Assume that there is a finite probability for tunneling of N from |1> to |2> , therefore:
1H 2=2H 1=V
Any state has to be a linear combination of the two basis states
= c1 1 c 2 2

What will be the energy for that state? Solve stationary Schrdinger equation!
H = E

We just calculate the scalar product with our two basis functions. First the left side:
1 H = 1 H

c 11 1 H c 22 = c1 1 H 1 c2 1 H 2 =c 1 E 0 c 2 V
2 H = 2 H c 11 2 H c 22 = c1 2 H 1 c 2 2 H 2 = c 1 V c 2 E 0
83

The right side of the equations gives us:


1 E = 1 E

c11 1 E c 22 = E c 1 11 E c 2 12 = E c1
2 E = 2 E c 11 2 E c 22 = E c 1 21 E c 2 22 = E c 2

This is nothing else than linear set of equations for c 1 and c2.
c 1 E 0 c 2 V = E c1
c 1 V c 2 E 0 = E c 2

Another, mathematical equal from to express this is based on matrices.

E0
V

V c1
c
=E 1
E 0 c2
c2

E 0 E
V

V
c1
=0
E 0 E c 2

The solution of the eigenvalue problem gives energy E and the c 1 and c2.
Non-trivial solutions are only possible if the determinant vanishes.
det

E 0 E
V

V
= E 0 E 2V 2 =0
E 0 E
84

As a result we find two solutions for the energy E:


E +=E 0 V
E - =E 0 V
The corresponding eigenfunctions are:
1 2
+=
2

1 2
- =
2

If V is positive, than the state with - will be the ground state, because its energy
is lower. The energy difference between both states is equal to 2V.

2V= =h f
Electromagnetic waves with frequency f can stimulate transitions between these
states.
For NH3 the frequency will be f=23.87012 GHz (=1.2559 cm) and defines the
Frequency standard for microwave technology.
NH3 is absorbing microwaves with that frequency very strongly.

85

9.2 Stark effect: Ammonia (NH3) in electrostatic field


State |1> : Dipole moment d in direction of electric field F.
State |2>: Dipole moment against direction of electric field.
This changes the energy E0 in the states: |1> by -F*d and |2> by +F*d

E 0 F d
V

V
c1
c
=E 1
E 0 F d c 2
c2

The energy of the stationary state is again given by the vanishing determinant.
det

E 0 F d E
V

V
= E 0 F d E E 0 F d E V 2= E 0 E 2 F d 2 V 2 =0
E 0 F d E

E + F = E 0 V 2 F 2 d 2

E - F = E 0 V 2 F 2 d 2

86

E + F = E 0 V 2 F 2 d 2

E - F =E 0 V 2 F 2 d 2

For small fields the energy changes quadratic with field, for large fields linear.
The change of energy in electric fields is known as linear and quadratic Stark-effect.
Even in case of rather larger electric fields like 10 kV/cm the change corresponds
to the quadratic Stark-effect. Compared to electric field strength in
atoms these are weak fields.
87

9.3 Qualitative understanding of chemical bonding


E - =E 0 V ,

E 0,

1 2
- =
2

anti-bonding

E 0,

bonding
1 2
E +=E 0 V , +=
2

Lets take two protons and one electron (H2+). The basis corresponds to electron at proton
one |1> or electron at proton two |2>. If the distance between the protons is small enough,
then there will be some probability for tunneling of the electron between the protons.
In contrast to the NH3 example, the sign of V changes to -V (Coulomb potential), so that
the symmetric state will be the ground state. The tunneling of the electrons lowers the
kinetic energy of the electron, so that the total energy will be lower.
This lowering of energies is the reason why chemical bonds form.
88

Why has this state a lower energy?


The total energy of the electron is the sum of kinetic and potential energy.
The electron would prefer to be close to the nucleus, because the Coulombpotential provides a negative potential energy. Unfortunately, this would
localize the electron in a small volume. Due to Heisenberg uncertainty relation the
spatial localization has to be compensated with an increased momentum. Now, the
square of the momentum goes into kinetic energy, which is always positive.
Having two protons available then tunneling between these two protons does
not localize the electron so much as before and it can access a lower potential
energy without paying with increased positive kinetic energy. The total energy
Of the system will be lowered which is the reason why chemical bonds form.

E
0

89

10. Angular momentum operator


classical Mechanic:

L =
r p

L x = yp z zp y
L y = zp x xp z
L z = xp y yp x

Quantum mechanic:
L =
r

y z
i
z
y

Ly =
z x
i
x
z

Lz =
x y
i
y
x
Lx =

grad
i

90

Rotations will not change the distance from origin.


--> use spherical coordinates (r, , )

z
r

x = r sin cos
y = r sin sin
z = r cos

x
We need to replace derivative with respect to x, y, z by there corresponding angular
derivatives.

x
y
z

x
y
z
= r sin sin
r sin cos
0
x
y
= y
x
= x
y
x
y
y
x

Lz =

91

Now, we calculate the eigenvalues of Lz :


Lz r , , =
Ansatz:

=
i

r , , = 0 r , e

i i
= 0 r ,
e
=
i
i
Rotation by 2 should not change the measurement
and + 2 should give the same result
e

= e

= e

1
i

2 = i 2 m = m

m = 0, 1, 2, ...

Lz m = m m

m: eigenvalues of Lz

m = 0(r, ) eim : eigenfunctions of Lz


92

Can we measure Lx and Ly sharp if we are in an eigenstate m ?


Only if the commutatot [Lx, Ly] is zero, one can measure both components sharp.

[ Lx , L y ]

= [ y p z z p y , z p x x pz ]

= y pz z p y z px x p z z px x p z y pz z p y
= y p z z px y p z x p z z p y z p x z p y x p z z p x y p z z px z p y x pz y p z x pz z p y
= y p z z px y z p z p x x z p z p y x p z z p y
= y pz z z p z p x x z p z p z z p y
= y [ pz , z ] px x [ z , pz] py
= y [ z , p z ] p x x [ z , pz ] p y
i

= i x p y y p x = i Lz

[ Lx , L y ]
[ Ly , Lz ]
[ Lz , Lx ]

= i Lz
= i Lx
= i Ly

The components of the angular momentum operator can not be


measured at the same time.
(Vector L can not have a fixed direction.)
93

Eigenfunctions of Lx and Ly are not eigenfunctions of Lz.


How to describe then angular momentum in QM?

L2 = L 2x L 2y L2z

[ L 2 , L z ]

= [ L 2x , L z ] [ L 2y , L z ] [ L 2z , Lz ]

0
= L L z Lz L L L z L z L 2y
2
x

2
x

2
y

L x Lz L x L x L z L x L y L z L y L y L z L y
=

L x [ L x , L z ] [ L x , L z] Lx L y [ L y , L z ] [ L y , L z ] L y

i L x L y i L y Lx i L y Lx i L x L y

L2 and Lz can be measured at the same time (common set of eigenfunctions)


If

A =a

and B = b then:

A B = A (b ) = b A = b a
B A = B (a ) = a B = a b
(A B B A) = (b a a b) = (a b b a) = 0
numbers
[A , B] = 0

(also true the other way around)

94

Eigenvalues of L2 are needed:


2

, L

L2 = 2

, L

, L

Lx , Lx

2
x

2
y

, L

L y , Ly

1
sin 1
2
sin

sin 2 2

2
z

Lz , Lz

L2 contains derivates with respect to both angles -> and m are not independent.
Ansatz:
r , ,

f r Y lm ,

Solving the differential equation (see any text book on QM) gives:

L2 Y lm , = 2 l l 1 Y lm ,

L z Y lm , = m Y lm ,
with l = 0 , 1 , 2 , 3 , . . .
m = l , l 1 , . . . , 0 , . . . , l

m l

95

10.1 Spherical harmonics

Y lm , = spherical harmonics)

2 l1 l m ! m
P l cos ei m
4 l m !
Lz
Legendre-Polynome (adjoint to) l+m
Y lm , =

1m
P x =
2l l !
m
l

m
2 2

1x

d lm
d x l m

l = 0

1
Y 00 , =
4

l = 1

Y 10 , =

l = 2

Y 20 =

1
2

Y 22 =

1
4

x 21

see Messiah, Nolting


s-state

3
cos
4

Y 11 , =

5
3cos 2 1
4

Y 21 =

3
sin ei
8

15
sin cos ei
8

15
sin 2 e2i
2

All spherical harmonics for m0 are complex!

96

historical names
l
l
l
l
l

=
=
=
=
=

0
1
2
3
4

l=0

s-state
p-state
d-state
f-state
g-state
(r,

sharp
principal
diffuse
fundamental

m=0
m = -1, 0, 1
m = -2, -1, 0, 1, 2
m = -3, -2, -1, 0, 1, 2, 3

,) = (r) no angular momentum, spherical symmetric

2
Classical picture for L und Lz

L2 2 l l 1
Lz

L moves on sphere
with radius

L l l1

l l1
Lz =
Lz = 0

l = 1,

radius 2

L z =
Lz fixed value, but smaller than the projection if the radius on L z
Lx, Ly have no fixed values

97

Do we need L2 for anything?


2
2
2
2
2
1
2

=
2 2 L
2
2
2
2
r r
x
y
z
r
r

11. Hydrogen atom


2
p
H =
U r
2
e2
U r =
4 0 r

= mass (in pace of m, because m is needed for qunatum


number m later on.

2
2
2 2
2
1 2
p
=
=

L
2
2
2 r2
r r
r 2 2

As usual, we search for stationary solutions H = E


The Hamilton operator commutes with Lz and L2, which means that the hydrogen
wavefunction must contain the already known spherical harmonics.
2
2,
[H ,
L ]=[ H , L z ]=[
L L z ]=0

98

Ansatz:

nlm r , , = f nl r Y lm ,

E nlm f nl r Y lm ,

2
2 f nl r
2 1
2
=

f nl r U r f nl r Y lm
2 l l 1 f nl r Y lm
2
2 2
2
r r
2 r
r

Differenzial equation for fnl(r) depends on l, but not on the angles itself.
E nlm

2
2 f nl r 2
2 l l1
f nl r =

f r U r f nl r
f nl r
2
r r nl
r2
2 r 2

There is no dependence on m -> Enl


We are interested in bound electrons, fnl(r -> ) = 0
fnl(r) = Ansatz as polynomial times exponent
= ea r [b nl cnl r d nl r 2 . . . ]
Inserting in differential equation gives constants -> a, b, ... -> done
nl

The wavefunction needs to be normalized so that the series has to be finite.


This gives a condition for allowed energies (see: Mathematica H-Atom.nb).

99

e
U r =
4 0 r

In particular for
E nl = E n =

1
E0
n2

no l dependence

e
1
E0 =
= 13,6 eV = 1 Ry
4 0 2 a0
2 4 0
10
a0 =
=
0,52917710
m
e2

Bohr radius

For a general potential the energy will depend on n and l, in case of


the Coulomb potential there is only a dependence on n.

Main quantum number


n = 1, 2, 3, . . .
Orbital quantum number
l = 0, 1, 2, . . . , n-1
Magnetic quantum number
m = -l, . . . , 0, . . . l
All ions with 1 electron like He+, Li++, . . . can be described in the same way.
Only the potential U(r) changes e2 -> Z e2
Z2
En = 2 E0
n

100

n=1

l=0

s - state

m=0

n=2

l=0

s - state

m=0

l=1

p - state

m = -1, 0, 1

l=0

s - state

m=0

l=1

p - state

m = -1, 0, 1

l=2

d - state

m = -2, -1, 0, 1, 2

n=3

1 state
4 states

9 states

Each state can be occupied by 2 electrons! (Reason is spin see later chapter)
n=1

K Shell

2 electrons

n=2

L Shell

8 electrons

n=3

M Shell

18 electrons

101

11.1 Radial wave part of hydrogen-like atoms


n=1
l=0

n=2
l=0 l=1

fnl(r)

r2fnl(r)2

n=3
l=0 l=1 l=2

fnl(r)

fnl(r)

r2fnl(r)2

r2fnl(r)2

x-axis is for all pictures the radial distance r in units of Bohr radius a 0.
The radial functions have n-l-1 zeros and may also become negative.

102

11.2 Construction of real valued angular functions


s-wavefunction is spherical symmetric (no angular dependence)

l = 0

Y 00 , =

1
4

All spherical harmonics for m0 are complex!


Building proper linear recombination one can construct completely real valued orbitals.
p-wavefunction

l = 1

Y 10 , =

3
cos
4

Y 11 , =

3
sin ei
8

p x=

1
1
3
3
3 x
Y 11 Y 11 =
sin ei ei =
sin cos =
4
4 r
2 8
2

py=

i
i
3
3
3 y
Y 11Y 11 =
sin ei ei =
sin sin =
4
4 r
2 8
2

p z=Y 10 =

3
cos
8

103

s-orbital l=0

p-orbital l=1

Alonso/Finn: Quantenphysik

104

the d-orbitals are constructed the same way:

l = 2

Y 20 =

1
2

Y 22 =

1
4

5
3cos 2 1
4

Y 21 =

15
sin cos ei
8

15
sin 2 e2i
2

d-wavefunction
m =0

d z r =

m =1

d xz

m =1

d yz

m =2

dx y =

m =2

d xy

5
2
3 cos 1
16
15
sin cos cos
4
15
sin cos sin
4
15
sin 2 cos 2
4
15
sin 2 sin 2
4

5
3z 2 r 2
16
r2
15 xz
4 r2
15 yz
4 r2
2

15 x y
2
4
r
15 xy
4 r2

105

d-orbitals l=2

Alonso/Finn: Quantenphysik

106

f-orbitals l=3

m=1

m=2

m=3

m=0

Many more plots and animations of orbitals and densities:


http://winter.group.shef.ac.uk/orbitron/

107

Summary

No planet like orbits


There exist bound states with negative energy

Z2
En = 2 E0
E 0 =13.605 eV
n
Solutions with positive energy correspond to scattering of electrons.

The complete hydrogen wavefunction depends on 3 quantum numbers n, l and m.

nlm
r =

Z3 2
a30 n2

nl1!
nl !

The wavefunctions are orthonormal:

2Z r
n a0

L 2l1
nl1

2Z r
2Z r
exp
Y ,
n a0
n a 0 lm

d 3 r n*' l ' m ' r nlm r

= n ' n l ' l m' m

Each l is degenrate with 2l+1 states. The degeneracy of quantum number n is:
n1

M n= 2 l 1=n

l=0

The ground state n=1 is non-degenerate, first excited state n=2 is 4 times degenerated
(2s and 3 2p states with equal energy). With spin one has to multiply the number by108
2!

Spektral lines

optical transition are governed by the dipole selection rules

l = 1

m = 0, 1

En/E0
n=3
n=2

n=1

An electron transition is always connected with emission or absorption of a photon.


Energy of the photon must exactly equal to the energy difference of participating
levels so that the transition can occur.

E = =2 =2 c /
1 E
Z 2 e2
1
1
1
1
=
=

=R

H
2
2
2 c 4 a 0 c n21 n22
n1 n2

For hydrogen gas have been several series observed (n1=1 Lyman, n1=2 Balmer).
109
RH=Rydberg constant

11.3 further approximation


Instead of the electron mass one should use the reduced mass.
1
1
1
1
=

M Kern
me
me

This allows to observe an isotope effect in optical spectra. Deuterium has been found
in 1932 measuring the Rydberg constant very accurately R H/RD=0.99973.

Fine structure: relativistic corrections (Spin-orbit-coupling, Dirac-equation)


Splitting observed in case of p, d and f-states.

Hyperfine structure: Interaction of electron spin with nuclear spin


Lamb-shift: Interaction with vacuum (quantum electrodynamics) gives additional
splitting (5eV) of the 2s1/2 and 2p1/2 states, which are degenerate in Dirac equation.

Fine structure constant


=

4 0 2
me

1 / 137

110
Fliebach:Quantenmechanik

12. Particles in magnetic fields


Electrodynamics: Charge Q moving in a circular orbit is the same as a
current in a loop -> magnetic Dipole
Magnetic moment M= current x area

r
v

Qv
Qmv
Q
r 2=
r=
rp
2 r
2m
2m
Q
Q

M=
r p =
L
2m
2m

The interaction energy of a magnetic dipole M with an external magnetic field B


is given by:

E =
M
B
111

QM treatment
Replace classical properties by corresponding operators:
Electron with charge Q=-e and mass me

e e
L
L

M=
L=
= B
2 me
2 me

Bohr magneton B=e/2me=9,27 10-24 J/T

The magnetic interaction can be described by an additional term in the


Hamilton operator which includes the interaction of the magnetic
moment of an electron with a magnetic field:
H =
M
B=

L
B

112

12.1 Normal Zeeman-effect


Assume hydrogen like atom in a magnetic field with U(r)=U(r)

B
B Bz

H = H 0
LB = H 0
Lz

[without loss of generality B=(0,0,Bz)]

Eigenfunctions of Lz are also eigenfunctions ofn H without magnetic


field, because [H0,Lz]=[H0,L2]=[L2,Lz]=0 (see H-atom)
Lz=m

mit m=-l, -l+1, ...,0, ...,l

Energy levels will then be:


Enlm=Enl + m B
Bz

113

normal Zeeman-effect
e.g. atom with d-electrons (d -> l=2)

Enlm=Enl + m B Bz
B Bz

E3d

m = +2
m = +1
m=0

(2l+1) degnerate states


wuth m = -l,+l

B=0

m = -1
m = -2
(2l+1) states with different
energy

B 0

Splitting in 2l+1 levels by an external magnetic field.

This is the reason for calling m magnetic quantum number.

114

Numebr of spectral
lines

m = +2

l=2

m = +1

E3d

m=0
m = -1
m = -2

B=0

E2p

B 0
m = +1

l=1

m=0
E+BB

m = -1
E-BB

Selection rules: l=1, m=-1, 0, 1


15 possible combinations, 9 transitons allowed by dipole selection rules
3 mesurable spectral lines, because the levels have equal energy distances.
115

13. Spin
Experimental facts:
1. Normal Zeeman-effect is the exception: Most often one
observes the anormal Zeeman-effect (additional
splittings)
2. Fine structure of alkali elements : Yellow D-line of Na is
a doublet instead of a single line.
3. Stern-Gerlach experiment

Pictures and information on Stern-Gerlach experiment are from


Physics Today December 2003: Friedrich and Herschbach,

"Stern and Gerlach: How a Bad Cigar Helped Reorient Atomic Physics"
http://www.physicstoday.org/vol-56/iss-12/p53.html

116

13.1 Stern-Gerlach experiment


(1921/1922)

An inhomogeneous magnetic field produces a force acting on a magnetic


moment, because F = - grad E
= M

F
B=

B
d Bz
L z B z =m B

dz

Therefore, particles with different magnetic quantum number m should


experience different forces, so that the beam should split.
117

Stern-Gerlachexperiment

W. Gerlach

Otto Stern

1.8.1889 Biebrich am
Rhein

17.2.1888 Sohrau
17.8.1969 Berkeley

10.8.1979 Mnchen

Physik-Nobelpreis 1943

Post card 8 February 1922 to Niels Bohr

Splitting in 2 beams in case of Ag, but no splitting in case of


Ag+.
The calculated magnetic moment for Ag equals 1 B.

118

Stern-Gerlach experiment for


hydrogen
Splitting observed in case of alkali elements, Ag, Cu,H
Phipps and Taylor, Phys. Rev. 29, 309-320
(1927)
The Magnetic Moment of the Hydrogen Atom

Problem: Splitting in two beams


l=0

-> 1 beam

l=1

-> 3 beams

l=2 -> 5 beams


So far, we would expect always:
Splitting of the beam in 2l+1 beams
No splitting in case of atoms in an s-like ground state,
e.g. hydrogen (n=1,l=0, m=0)

119

13.2 Explanation of the Stern-Gerlach


experiment
1925 by Uhlenbeck and Goudsmit after an idea of Pauli:
Elektrons have a permanent magnetic moment = spin
In complete analogy to angular momentum we
define spin operators with spin quantum
numbers s and ms.
1
s= ,
2

sm s s

m s

1
2

S =S x , S y , S z

Lz Y lm ,=m Y lm ,

L2 Y lm ,=l l 1 2 Y lm ,

1
S z s , m =m s s , m = s ,m
2
3 2
2
2

S s , m =s s1 s , m = s , m
4
s

Also identical commutator


relations:
[ S x , S y ]=i S z

[ L x , L y ]=i L z

120

Goudsmit

Uhlenbeck

Pauli

13.2 Pauli matrices


Possible representation of S using Pauli matrices = (x,y ,z):

z=

1 0
0 1

x=

0
1

1
0

y=

0 i
i 0

S=

These matrices fulfill all commutator relations (home work :-).


The wavefunction becomes a vector with two components (spinor).

= 1 r ,t

1
0
2 r ,t
= 1
r , t + 2
r ,t 0
1
121

Using the matrices the Hamilton operator becomes itself matrix form.

H=

H0
0

0
eB L z

2m 0
H0

0
Lz

e
B 1 0
m2
0 1

Quantitative analysis of experiments


The total angular momentum is given by vector addition of orbital
momentum and spin J=L+S. The total magnetic moment is however
not proportional to J, but is given by:
e
e
= e
M
L
S =

L g
S
2m e
me
2m e

The Land-factor g is for an electron equal to 2 within relativistic Dirac


theory. Quantum electrodynamics gives g=2.00231930437... 2
(1+/2 + ...).
122

Anormal Zeeman-effect: Spin-orbit + Zeeman


H SO=
S
L

l = 1 s = 1/2

Spin-orbit

Zeeman

j = 3/2

mj
mj
mj
mj

=
=
=
=

3/2
1/2
1/2
3/2

mj = 1/2
mj = 1/2
j = 1/2

l=0

mj = 1/2

s = 1/2
j = 1/2

mj = 1/2

Quantum numbers mj (j-j coupling) important for elements with large proton
number.

123

13.4 Complete set of quantum numbers for H-atom


Hamilton operator for H-atom im magnetic field:
B

H = H 0
B
L g
S

To describe a state of the H-atom uniquely, we need the main


quantum number n, orbital quantum number l, magnetic quantum
number m and spin quantum number ms.
n l m m
r = R nl r Y lm , m
s

1/ 2 =

1
0

1/ 2 =

0
1

The spin functions are independent on position and time. The spin
represents a fundamental property of the electron, which has no
classical counter part.
124

13.5 Fermions and


Bosons

Not only electrons have a spin but also neutrons, protons, positrons etc.
Particles with half-integer spin are called Fermions, with integer spin
bosons.
Fermions: e, n, p, e+ (s=1/2), - (s=3/2)
All matter is build from fermions!
Bosons: photon (s=1), graviton (s=2)
All interactions are exchanged by bosons!

Spin can be a result of vector addition of spin of several particles.


(e.g. nuclear spins s=3/2 state of

57

Fe)
125

13.5 Fermions and


Bosons

Not only electrons have a spin but also neutrons, protons, positrons etc.
Particles with half-integer spin are called Fermions, with integer spin
bosons.
Fermions: e, n, p, e+ (s=1/2), - (s=3/2)
All matter is build from fermions!
Bosons: photon (s=1), graviton (s=2)
All interactions are exchanged by bosons!

Spin can be a result of vector addition of spin of several particles.


(e.g. nuclear spins s=3/2 state of

57

Fe)
126

13.6 Spin and statistic: Pauli principle


Bosonic particles can occupy a single particle staremany times and are
described by symmetric wavefunctions.
Fermionic particles are described by anti-symmetric wave functions and
can not occupy a single particle state twice.

Pauli-Principle: Fermionic particles can not be equal in all


quantum numbers.

One major result of Pauli principle is an explanation of the order in the


periodic table of elements.

127

13.6 Spin and statistic: Pauli principle


Bosonic particles can occupy a single particle state many times and are
described by symmetric wavefunctions.
Fermionic particles are described by anti-symmetric wave functions and
can not occupy a single particle state twice.

Pauli-Principle: Fermionic particles can not be equal in all


quantum numbers.

One major result of Pauli principle is an explanation of the order in the


periodic table of elements.

128

14 Periodic table
14.1 Atoms with many electrons
En/E0

1
E n = 2 Ry
n

ground
H
He
Li
oder
Be

n=3
n=2

n=1

state
(1s)1
(1s)2
(1s)2
(1s)2
(1s)2
(1s)1
(1s)2

(2s)1
(2p)1
(2s)2
(2s)1
(2p)2

(2p)1

Something has to be different to the H-atom!


Improved approximation:
Each electron interacts with the positive nucleus with Z protons and
interacts with the other Z-1 electrons of the atom.
Potential U(r) is not the Coulomb potential anymore!
129

However, then there are no analytic solutions possible. One has to use approximations
and numerical methods. Result: Enl instead En , Enl increases mostly with l.
Degeneracy for l lifted.
Degeneracy with respect to m remains.

En/E0
n=3

Li (1s)2 (2s)1 unique configuration

n=2

n=1

Until Ar (Z = 18) the periodic table behaves normal, then however one finds
E3d E4s
3d states can be above or below with respect to the 4s states
Similar for 4d above/below 5s, 5d above/below 6s
anomal occupation of side group elements
4f (lanthanide) and 5f (actinide) show anormal behavior.
Many-body effects and relativistic correction will deliver the correct ordering.
130

Clemens Winkler, Prof.


In chemistry at
Bergakademie Freiberg
finds in 1886 the
element Germanium in
the mineral Argyrodit
mined at Grube
Himmelsfrst close to
Freiberg.

Orginal work of Mendelejew 1869 on the periodic table.


131

l=0 (s)

l=1 (p)

l=2 (d)

l=3 (f)

siehe auch http://www.iap.uni-bonn.de/P2K/applets/a3.html

132

15. Many-body systems (bosons and Fermions)


So far: 1 particle in state
In order to measure the position we place a detector with volume dV at r.
Probability to detect particle: dW = |(r)|2 dV

15.1 distinguishable particles


Two distinguishable particles A, B (e.g. electron and neutron)
We need two detectors, located at rA and rB
Probability, that both detectors react at the same time
dW = |(rA, rB)|2 dVA dVB
Probability to find particle A at rA
dWA = dVA |(rA, rB)|d3 rB
133

Sum over all possible positions rB for particle B, because B can anywhere in
space.
Similar: Probability, to detect particle B, without being interested in particle A.
dWB = dVB |(rA, rB)| d3 rA
Spin will not really change the discussion, but will just add an additional degree of
freedom:
2T : , , ,
(rA, rB) -> (rA,sA, rB,sB)

dW A = dV A

rA , s A , rB , s B d 3 rB
sA

sB

Up to now there was not really anything new. This is fully in accord with our
classical expectations.

134

15.2 Two identical particles (electrons)


Instead using A, B we will label the electrons with 1 and 2
at r1 we have positioned detector 1 with dV1
at r2 we have positioned detector 2 with dV2
If both detectors give a signal at the same time, then we know that there has
been an electron at r1 and at r2.
Which electron created the signal at detector 1? Was it electron 1 or electron 2?
This question can not be answered, because electrons are really
indistinguishable particles, they are absolutely identical.
The main difference in quantum mechanics is, that the two-particle
wavefunctions (r1, r2) and (r2, r1) may be different.
(r1, r2):
(r2, r1):

first electron at r1 and second electron at r2


other way around

135

Based on the experiment it has to hold that:


2

r1 , r2 = r2 , r1

Even if the squares are equal, we have two possible solutions for the
wavefunctions which differ in sign.
A) Symmetric wavefunctions
(r1, r2) = (r2, r1)
(Symmetric functions remain symmetric by additions and multiplication with
scalars.)
This solution corresponds in nature to particles with integer spin (0, 1, 2, ...).
(e. g. pion, He, photonen, . . . = Boson)
In particular the many-body wavefunction can be a product of single-particle
states.
r1 r2 = r1 r2
Bosons can occupy single-particle states several times.
(Bose-Einstein-condensate: Nobel prize 2001)

136

B) anti-symmetric wavefunction
Particles with half-integer spin (s = , 3/2, . . . )
e.g. electron, proton, myon, neutrino, . . .
= Fermion
Spin state is important here!
(r1, s1, r2, s2 ) = -(r2, s2, r1, s1)
The anti-symmetric behavior of the many-body wavefunction under particle
exchange is nothing else than the well known Pauli principle.
It is not possible to have a fermionic state given by a product of one-particle
states

r1 s1 , r2 s2 = r1 , s1 r2 , s2
r2 s2 , r1 s1 = r2 , s 2 r1 , s1
= r1 , s1 r2 , s2

1 = -1
=0

Fermions can not occupy the same single-particle state several times. ||
2
=0
Periodic table of elements

137

Hydrogen atom n, l, m, s
He: 1s
+

n, l, m are equal but s is different

allowed
forbidden

allowed

r
because 1

allowed

und

2
r

a
depend on different arguments
2

138

15.3. Generalization to many particles


Notation: r1, s1 = 1
r2, s2 = 2
etc.
Definition: Transposition operator (exchange of two particles)
12(1, 2, . . ., N) = (2, 1, . . . ., N)
(83 exchanges 8 with 3)
1212 (1, 2, . . . ,N) = 2 (1, 2, . . . ,N) = (1, 2, . . . ,N)
Eigenvalues needed:

= = =
= 1
= 1
= *
Operator is self-adjoint and unitary
(2 = 1 = -1 * = -1 )
Eigenvalues of select between symmetric and anti-symmetric wavefunctions

139

Boson: Every particle can be exchanged with any other particle

B 1,2 ,3= [ 1,2 ,3 1,3 ,2 3,2 ,1 2,1 ,3 3,1 ,2 2,3 ,1 ]


The bosonic wavefunction B has to be normalized.

In general one can build a bosonic many-body wavefunction by permutating


all coordinates.

B=

140

Fermion

F = [ 1,2 ,3 1,3 ,2
2,1 ,3 2,3 ,1
3,1 ,2 3,2 ,1 ]

() = character of permutation
+1

F =

-1

for even number of exchanges


for odd number of exchanges

This will give determinants, if is expressed


as product of single-particle functions.

141

H =

Hi
i

= 1 1 2 2
H i i = E i i

N=2

1
1 1 2 2 2 1 1 2
2

1 Just from normalization if the single-particle


1 1 1 1 2
=
2 wavefunctions are normalized.
2 2 1 2 2

F =

N=3

F
N

1 1 1 2 1 3
1
=
1 2 2 2 3
3 ! 2
3 1 3 2 3 3

1 1 1 N
1
=
N ! 1 N
N
N

are called Slater-Determinants

142

Helium atom: 2 electrons


2

p
p
H = 1 2 V r1 V r2 V r1 r2
2
2
Coulomb-interaction
Assume the solution, H = E is known

= r1, s1 , r2 , s 2 = 1,2
We want to proof that it holds: H = E
H 1,2 1,2 = E 1,2
1 <-> 2 exchange

H 2,1 2,1 = E 2,1 = E [ 1,2 ]


Further, it is true that
H 1,2 = H 2,1
H 2,1 2,1 = H 1,2 2,1 = H 1,2 1,2
H =E = E
(1 H ) =E =H
1
H =H
H = H

[ H , ]=0

143

[ H , ]=0
The Hamilton operator H and the operator exchanging particles commute,
which means they have a common set of eigenfunctions.
Eigenfunctions have either to be symmetric (boson) or
anti-symmetric (Fermion).
A particle or system of particles will be either a fermion or a boson.
There will be no mixed character (part boson and part fermion) possible.
There is no superposition of fermionic and bosonic wavefanctions allowed.

144

16. Approximate methods


He-atom has 2 electrons
2

H =

2
2
p 2i
Ze 1
e
1

2 4 0 ri
4 0 r1 r2

i=1

Hi

H = H i
i

Coulomb-between electrons

1
V
2 i j ij

What are the stationary solutions ?

H =E

The solution for independent particles (no e-e interaction) is known form
the solution of the Hydrogen atom.
However, the e-e interaction depends on the position of both electrons.
This does not allow for separation of the problem. For a small number of
. problem exactly.
electrons one can use numerical methods to solve the
The numerical complexity and demand increases exponentially with
number of electrons, so that one needs approximate methods to find a
solution for realistic problem sizes.

145

Why do we need approximate methods?


Example oxygen: O has 8 electrons
The many-body wavefunction depends on position of all 8 electrons.

r1 , r2 , r3 , r4 , r5 , r6 , r7 , r8

24 coordinates

To save the wavefunction we need as function of 24 coordinates.

10 values per coordinate


1024 values

8 bytes per entry


1025 bytes

8.5*109 bytes per DVD


1015 DVD's

10g per DVD


1010 tons
If there would be a method which would need only the charge density instead of the full
many-body function the problem would be orders of magnitude easier to handle.

(r) -> 103*8 byte ~ 8 kbyte


Nobel prize Chemistry 1998: Walter Kohn and John Pople.
Density Functional Theory = DFT
The total energy is a functional of the electron density.
Walter Kohn

John Pople

146