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Notas sobre teoría cuántica de la Univ. de Freiburg

- linDiffEq
- Electronics Honours Ug
- Quantum properties and Gravitational Field of a Field with Oscillation in Time
- TAYL08-248-286.I
- grerewiew
- Robbin and Salamon, Spectral Flow
- Fhtads as
- A theoretical introduction to wave mechanics
- Schrödinger Representation – Schrödinger Equation
- 1401.7018
- 2013.01.30-ECE595E-L10
- quantum mechanics
- Introduction to Quantum Mechanics 36-65
- Model for the Findings About Hologram Generating Properties of DNA
- Neutrino Oscillation
- Modern.pdf
- Wave–Particle Duality - Wikipedia
- 7 Quantum and Particle Physics
- Kaluza Klein
- The Photoelectric Effect

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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

It is strongly recommended to check all derivations and

Formulas themselves.

.

Please send any corrections and comments to

Jens.Kortus@physik.tu-freiberg.de

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

Atomic construction (STM -> move single atoms)

Theoretical predictions of materials properties

Computer aided molecular design (pharmacy, dyes)

(111)

atom

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

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

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]

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

an integer number times there

wavelength/2 into the box.

using cos2 +cos 2 +cos2 =1

n21 +n22 +n23 =(2 a )2 =(2 a c )2 =c

= 2ac (n21 +n22 +n23 )

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

-> UV catastrophe: intensity diverges for small ->

Classical physics is giving a wrong result here!

Wien law:

3

~ e

=h/ k

we need a mix of both radiations laws

* 23. April 1858 in Kiel

4. Oktober 1947 in Gttingen

Nobelpreis 1918

h

kT

e 1

h /kT

h

kT

large(e

1): e

x

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

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

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

Ernest Rutherford

1st Baron Rutherford of Nelson

August 30, 1871 October 19, 1937

Nobelpreis Chemie 1908

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

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.

Albert Einstein

* 14.3. 1879 Ulm

18. 4. 1955 Princeton

Nobelpreis Physik 1921

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

a) Wave character of light

Interference and diffraction (Huygens 1678)

Haag

8. Juli 1695

Double slit

Er = E1 E2

Intensities can not be superposed. Picture is not sum of single pictures

2

2

2

2

I = ErEr =Er =E1 E2 E1 E2

-> see photo-electric effect

12

Broglie * 15. August 1892 in Dieppe,

Normandie

19. Mrz 1987 in Louveciennes

Nobelpreis Physik 1929

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).

13

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

particles

only 1 open

only 2 open

both open

waves

How about electrons?

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

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

.html

14

1927 Electron diffraction using a Ni-crystal (Davisson & Germer)

1961 Double slit experiment with electrons

Claus Jnsson, Tbingen, Zeitschrift fr Physik 161, 454 (1961)

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

16

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

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=*

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

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

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

E r

1 2

, t = 2 2 E r , t

c t

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

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 ...

-> 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 /

momentum has a well defined

wave length.

de Broglie 1924

21

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

2

2

1 m0 c

2

= 2

c t2

22

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

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

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

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

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

|(r,t)|2 = 1/V

The probability is equal in all points of space.

26

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

Eigenvalue equation from linear algebra

a 11

a 21

a 12 x 1

= x 1

a 22 x 2

x2

A x= x

A) momentum measurement for plane waves:

pop = grad = p

i

r ,t = 0 e i kr t

p =

k nach de Broglie

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

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

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)

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)

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

30

*

*

*

=

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

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

Average of the property A is also called expectation value

A =

A = a w a

a

f A= f a w a

a

f A = f a w a da

a

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

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).

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

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

1

2

sin = 1cos2

2

x/L

x/L

36

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

37

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.

38

2 2

2

2

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

2

2

2m x

y

z

L3

L1

L2

0, y , z = L1, y , z = 0

x ,0 , z = x , L 2, z =0

x , y ,0 = x , y , L3 =0

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

39

classical Mechanic

Reflexion, Scattering

U0

U0

I

II

0

-> 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

k 1 =k 3 =

1

2m E

k 2=

1

2m E U 0

40

classical Mechanic

Reflexion, Scattering

U0

U0

I

II

0

-> 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

k 1 =k 3 =

1

2m E

k 2=

1

2m E U 0

41

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

-> 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

2

A3

admission coefficient D=

A1

B1

reflexion coefficient R=

A1

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

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

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

45

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

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 only if = 0

, are orthonormal, if

, =

0

1 =

, =

48

Additional requirement of completeness

Very important for mathematicians but any complex vector space can be completed

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

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

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

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

bra = <|

ket=|>

51

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

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

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

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:

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

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

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

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,) = (,)

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) = (,)

1)

, x = d 3

r *

r x

r

= d 3 r x r * r

= 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

= d r

r r =

, = p x

i x

i x

3

59

px =

i x

p =

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

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

Charles Hermite

* 24. Dezember 1822 Dieuze (Lothringen)

14. Januar 1901 Paris

62

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

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

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

64

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

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

,

= ,

, 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 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

1 ,[ A , B ]

A B

4

,

1

[ A , B ]2

4

2

A B

1

[ A , B ]

2

67

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

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

-> x =

Location is completely undetermined.

Slit

y

y

py = 0

y =

-> px = not possible no

69

px

Harmonic Oscillator:

x

x

U

E

k 2

x

2

2

px

U

2m

Origin x = px = 0 corresponds to rest position.

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

px

x

E min =

k

m

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

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.

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

Hn

( )

H n x

d y

= 1 e

ne

dy

n

1

Energy eigenvalues E n = (n+ )

2

72

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

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 =

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

a new operator.

N = A +A

N is hermitian

occupation operator

N n = nn

n

= 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

_ = 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

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

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

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

1 = A+ 0

1

+ n

n =

A 0

n !

En

A +n =

n1 n1

An =

n n1

equal energy distance

n = 0, 1, 2, positive integer

1

= n

2

2

Zero point energy

E0 =

1

E0 =

2

x px =

2

79

~ nx m =

*n x m dx

odd function vanishes.

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

80

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

Quantum electrodynamics is formulated usually in terms of creation and annihilation

operators, which means is based on the physics of the harmonic oscillator.

81

9.1 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

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

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

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

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

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

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

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

--> 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

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

92

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

measured at the same time.

(Vector L can not have a fixed direction.)

93

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

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

94

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

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

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

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

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

2

2

2

2

2

1

2

=

2 2 L

2

2

2

2

r r

x

y

z

r

r

2

p

H =

U r

2

e2

U r =

4 0 r

number m later on.

2

2

2 2

2

1 2

p

=

=

L

2

2

2 r2

r r

r 2 2

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

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

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

the Coulomb potential there is only a dependence on n.

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

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

s-wavefunction is spherical symmetric (no angular dependence)

l = 0

Y 00 , =

1

4

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

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

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

107

Summary

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.

nlm

r =

Z3 2

a30 n2

nl1!

nl !

2Z r

n a0

L 2l1

nl1

2Z r

2Z r

exp

Y ,

n a0

n a 0 lm

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

l = 1

m = 0, 1

En/E0

n=3

n=2

n=1

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

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.

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

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.

=

4 0 2

me

1 / 137

110

Fliebach:Quantenmechanik

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

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

Hamilton operator which includes the interaction of the magnetic

moment of an electron with a magnetic field:

H =

M

B=

L

B

112

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

B

B Bz

H = H 0

LB = H 0

Lz

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

Lz=m

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

wuth m = -l,+l

B=0

m = -1

m = -2

(2l+1) states with different

energy

B 0

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

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

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

(1921/1922)

moment, because F = - grad E

= M

F

B=

B

d Bz

L z B z =m B

dz

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

Ag+.

The calculated magnetic moment for Ag equals 1 B.

118

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

l=0

-> 1 beam

l=1

-> 3 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

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

relations:

[ S x , S y ]=i S z

[ L x , L y ]=i L z

120

Goudsmit

Uhlenbeck

Pauli

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=

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

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

theory. Quantum electrodynamics gives g=2.00231930437... 2

(1+/2 + ...).

122

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

Hamilton operator for H-atom im magnetic field:

B

H = H 0

B

L g

S

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

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!

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

57

Fe)

125

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!

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

57

Fe)

126

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.

quantum numbers.

periodic table of elements.

127

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.

quantum numbers.

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

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

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

In chemistry at

Bergakademie Freiberg

finds in 1886 the

element Germanium in

the mineral Argyrodit

mined at Grube

Himmelsfrst close to

Freiberg.

131

l=0 (s)

l=1 (p)

l=2 (d)

l=3 (f)

132

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

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

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):

other way around

135

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

+

allowed

forbidden

allowed

r

because 1

allowed

und

2

r

a

depend on different arguments

2

138

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

The bosonic wavefunction B has to be normalized.

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 odd number of exchanges

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 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

142

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

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

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

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

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

1024 values

1025 bytes

1015 DVD's

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.

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

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