QM II

Pascal Debus

ETH Z urich, Fr uhjahr 2013

Zusammenfassung

Approximation methods for stationary problems

standard QM problem: Given | (t0 ) , wanted : | (t) = U (t, t0 ) | (t0 ) U = e for time independent H U = e
i i

(continuous spectrum also understood.) We want |n and En with (H0 + V ) |n = En |n let

(0) (1) (2) En = En + En + 2 En + ... (0) (1) (2) |n = |n + |n + 2 |n + ...

H (tt0 )

seems obvious, but assumption. (convergence?)

H (tt0 ) (0) (0) H0 En |n + (0) (1) H0 En |n

nd eigenvalue and eigenstates (diagonalize H ) but: most problems cannot be solved exactly nd approximate solution.

+ 2

(0) (2) (1) (1) (2) H0 En |n + V En |n En

+ O 3 = 0 with O(1) step 0, O() step 1, O(2 ) step 2.

1.1

Time-independent perturbation theory, non-degenerate case

Step 0: Step 1

nothing to do multiply by m |
(0)

Assume:

H = H0 + V with H0 the Hamiltonian that I can solve (free Hamiltonian) and the perturbation V small and a dimensionless bookkeeping par. 0 1 H H0 full H

(0) (0) (0) (0) (1) (0) m H0 En m + m V En m =0 (0) (0) = Em En (0) (1) (0) (0) (1) m |n + m V m En mn = 0

to get |n
(1) |n =

(1)

(0) (0) (1) m |n |m m

m V m =
m

(0)

(0) (0) (0) (0) (1) + |m + |n n |n

En Em

(0)

(0)

We know
(0) (0) |n , En

from normalization
!

with
(0) (0) (0) H0 |n = En |n (0) (0) (0) (1) (1) (0) n |n = 1 = n n + n |n + n |n + O 2 1 0

with
(0) (0) n m = mn
pdebus@student.ethz.ch

has to be small. If (0) sec 1.2 if En 1

(0) (0) En = Em degeneracy! (0) Em quasi degenerate

step 2
(0)

take O(2 ) terms k |

(2) k |n + k (0) (0)

(0)

1.2
V k
(0) (0)

Time-independent perturbation theory: degenerate case

(0) Ek En

(1) (1) (2) En k |n = En kn (0) Assume En is -fold degenerate i.e. (0) (0) (0) H0 |n = En |n , i

for k = n 1i
(0) (2) (0) = V n En = n m=n 2 Vnm m=n (2) (0) n

(0) n (0) En

(0) m

(0) m

(0) Em

x
(0) (0) n |nj = ij i

En Em

(0)

(0)

Any linear combination

Note En < 0 for ground state. Next compute |n

(2)

|(0) = n
i=1

(0) cni |n i

: initially x normalization such that

(0) (i) n n = i0

is

an eigenstate E ()

of

H0

with

evaluation

En

(0)

this is in conict n n = 1 sort out at the end.

(2) |n = k=n

En1 En
(0)

En2 . . . Enk

|k

(0)

(2) k |n +0

(0)

=
k=n (1) (0) |k

(0) (0)

V k

(0)

En Ek

(0)

En

(1)

k |n

(0)

(1)

= 0, H0

= 1, H

En Ek

(0)

(0)

Typically V lifts degeneracy at least partially since often [H0 , V ] = 0 Pick one of the evals Enk with H |nk = Enk |nk

plug in |n

and sort out normalization |n

N

= Z1/2 |n

x such that
N

n n M = 1

for 0: Enk En and

(0)

then
N

|nk |nk (0) = n n N

(0) (1) (2) (0) (1) n | + n | + 2 n | |n + |n + ... i=1

(0) cnk i |n i some lin comb

= 1 = Zn n |n = Zn

have to nd good linear combination, i.e. coe cnk i . Main idea as before:
(1) |nk = |(0) nk + |nk

(2) (1) (1) = En kn = Zn 1 + 2 n |n + O 3 1/2 Z n =1

2 (1) (1) |n O 3 2 n

(0) (1) (1) 0 = H0 E n |n + V En |(1) nk k k

with
(2) |n

=
k=n m=n

(0) |k

... Vkm Vmn

(0) (1) |n = k

dim(H0 )

... 1 2
(0)

an |
=1

(0)

En Ek
(0) |n

(0) 2 Vkn

Em En
(0)

(0)

Vkn Vnn En En
(0) (0)

and
(0) cnk i |n i

k=n

En Ek

(0)

i=1

multiply by nj |.
dim H0

(0)

then
(0)

E
=1

(0)

(0) (0) En an n | j

| H | =
m,n

c m cn m | H |m =
m,n

c m cn En m n
mn 2

=0 for n=

=0 for n=

=
n

cn

En E0
n

cn

= E0

+
i=1

(0) (0) (1) (0) (0) (1) (0) (0) En |ni En V n n cnk i n n |ni j j j j k k
Vji ij

Harmonic oscillator H= d2 m 2 2 x 2m dx2 2

2

solve (1) V11 Enk V21 det . . . V1

V12 V22 . . .
(1) Enk

...
(1)

V1 . . ... . =0 . .. . . . (1) . . . V Enk

...

(of course we know E0 = 2 ). Let (x) = Aebx since =1= compute | H | = A

2 2 !
2

eq. of order in Enk solutions

dx A

2 2bx2

= A

2b

1.3

easy way out (sometimes)

if Vij = 0 for i = j problem already solved solutions are

(1) En i

dx ebx

d2 m 2 2 bx2 x e = ... 2m dx2 2

2

(0) i

(0) i

b m 2 + = | H | E0 2m 8b

Note: if operator A with [A, V ] = 0 and

(0) (0) A|n = ani |n i i

Minimize with respect to b

2 m 2 d | H | = =0 db 2m 8b2

with ani = ank , then these

(0) |ni

bmin =

m 2 2

k=i E0 | H |
min

are good eigenstates

(0) (0) (0) (0) n [A, V ] n V n = 0 = (ani ank ) n i i i i =0 Vik

in this case we get E0 exactly is a coincidence, since Ansatz=true wave function.

Vik = 0

1.5

WKB approximation, semiclassical approximation

1.4

The variational principle

WKB for Wentzel, Kramers, Brillouin (see QMI Ch. 8.3.) useful for 1-dim problems with smooth popential. Schr odinger: if d2 V (x) (x) = E (x) 2m dx2
2

Useful to get good estimate of ground-state energy E0 of complicated systems. Claim E0 if | normalized. Let | H | = | H | |

V (x) V0 const. | = cn |n ( x) = e
i

H |n = En |n =1 cn
2

2m(E V0 )x

if V (x) is slowly varying. Ansatz =1 ( x) = e 3

i

S (x)

Ansatz into Schr odinger: i 1 2 S + (S ) + V (x) E = 0 2m 2m equivalent to but more complicated than Schr odinger. Note for V (x) V0 S = 2m (E V0 ) x and S =0 rst term vanishes for V (x) V0 Let S (x) = S0 (x) + S1 (x) + O( 2 ) plug in into dierential equation for S 1 2 (S ) + V (x) E = 0 2m 0 S0 = 2m (E V (x)) p(x) 1 S0 S1 S0 = 0 2 i S0 i p (x) S1 = = 2 S0 2 p(x) solve these dierential equation
x

2.2

Spin-orbit term

naive derivation (1) Electron with spin magnetic dipole moment = e g s m2 e = r2 T 2 s= mr2 T g (from Dirac)

(classical limit)

(2) Electron feeds magnetic eld due to the proton E e r r3 1 L 1 E = 2 3p r = c2 mc r mc2 r3

B=

wrong by factor 2 (Thomas precession) . . . correct result HSO = To describe spin |n, , s = 1 , ms 2 = n
m ms

Ze2 1 L S, 2mc2 r3

( B)

= n

(r, ) ms

with ms spin-orbit dx p(x ) 1 0 0 1

S0 = S1 =
i

i ln p(x) 2

(x) = Ae (S0 + 1 ) i A+ = e dx p(x)

Note : HSO mixes states with same , but dierent m , m use degenerate perturbation theory with 2 (2 + 1) 2 (2 + 1) matrix + A p(x) e
i

p( x )

dx p(x )

spin

n, , m , ms | HSO |n, , m , ms diagonalize recall degenerate perturbation theory nd good linear combination that diagonalize this matrix by looking for symmetry use total angular momentum J L+S

2
2.1

The hydrogen atom

Basics

Two body problem proton (1)-electron (2)

2

H= new variables

2m2

2 1

for 2 2 + V (r1 r2 )

=0 j= 1 2 , for

1 =0 j= 2 . Use states

2m2

|n, , j, mj

R=

m2 r1 + m2 r2 m1 + m2 r = r1 r2

|n, , j, mj =
m ,ms

|n, , m , ms n, , m , ms n, , j, mj
Clebsch-Gordan

M = m1 + m2 m1 m2 m= m1 + m2
2

use J 2 = L2 + 2 L S + S 2 1 2 LS = J L2 S 2 2

H=

2M

|n, , j, mj are eigenstates of H0 , L2 , S 2 , J 2 , Jz

First few states =0 n=1 =1 =2 degeneracy 2n2

with eigenvalues En ,
2

ESO for =0

4 = n, , j, mj | HSO |n, , j, mj

( + 1) ,

23

j (j + 1) , mj

=0 n=1 n=2

=1
1 {2} 1S 2 1 {2} 2S 2

=2

degeneracy

2S 3 {2} 1 {2} 2S 2 2

ESO = 0 for =0 1 1 2 Ze2 n, , j, mj | 3 J L2 S 2 |n, , j, mj 2 2 2m c r 2 2 Ze2 1 3 = j (j + 1) ( + 1) 2 2 3 2m c r 2 4 = En (Z) 2n +

2 1 2

Fine structure partially lifts the degeneracy but for instance 2S1/2 and 2P1/2 are still degenrate.

ESO =

2.5

Corrections beyond ne structure

1 +1 1

j= + j=

1 2 1 2

Hyperne structure e eect of proton spin sp p = 2m gp sp , where the expep rimental value for gp is given by gp = 5.59 (not 2, sicne the proton is not a fundamental particle)) p induces B-eld and e feels the B-Field B. EHfs Z 4 4 We introduce the total spin F P = Se + Sp = ADD 21cm line PICTURE The Lamb shift (needs QED) leads to a modication of the Coulomb potential which splits 2S1/2 and 2P1/2 with ELamb (Z)4 (log Z)1 1 0 = Singulett Triplett me mp

2.3

Darwin term

Sloppy consideration electron position uctuates by r c mc electron feels average potential V (r + r) = V (r) + 1 r r V 2

correct result is
2

HD = only for = 0!

8m2 c2

2 V =

2 Ze2 (r ) 2m2 c2

ED = n, , j, mj | HD |n, , j, mj (Z) = En n
2 0

2 Ze2 n (0) = 2m2 c2

3
2

Many Electron Atoms

Consider an atom with N electrons

N

H=
i=1

Ze2 p2 2m ri

+
i>j

e2 |ri rj |

2.4

Fine structure of Hydrogene

e-e-interaction

Combine E(l) , ESO and ED Enj =

2 2 (0) Z En n2

H (1, . . . , N ) = E (1, . . . , N ) n 3 1/2 4 j

1 : r1 s1

3.1
valid for l = 0, i.e. j = 1/2 and j = l 1/2. (0) Fien structure suppressed (Z)2 rel. to En only depends on j (not independtly on l and s) Notation for states:nLj n = 1, 2, . . . L = S (l = 0), P (l = 1), D(l = 2), ; F (l = 3) 1 J = l total anuglar momentum 2

Identical Particles

Consider N identical particles with Hamiltonian H (1, . . . , N and wave fucntion (1, . . . , N with 1 = r1 , s1 , . . . (position, spin, other quantum numbers...) Classical mechanics: We can always distinguish these N particles. A B A B

Quatum mechanics: We cannot keep track of individual particles if their wave functions ovelap. Dene an Operator Pij interchanging i j Pij (1, . . . , i, . . . , j, . . . N ) = (1, . . . , j, . . . , i, . . . N )
2 Pij =1

bosonic case: 1 1 (p(1)) . . . N (p(N )) S (1 . . . N ) = N ! P SN fermionic case: 1 A (1 . . . N ) = (1)P 1 (p(1)) . . . N (p(N )) N ! P SN A can be written as Slatter determinant: 1 A (1 . . . N ) = N! 1 (1) . = det . . N (1) .. . 1 (N ) . . . N (N )

Eigenvalues 1

As a cosnequence of indistinguishability H must be invariant under i j : [H, P ij = 0 There are N ! permutations of elements 1 . . . N which fall into 2 classes, even and odd. even sgn(p) = +1, (1)p : even number of interchanges odd sgn(p) = 1, (1) : odd number of interchanges We have [H, P ] = 0 P is a unitary Operator since | = P |P = |P P | P P = 1 For any oberservable A we have [A, P ] = 0 (identical particles cannot be distinguished by measurement)
p

Pauli Exclusion Principle Two identical fermions with the same quantum numbers (including spin) cannot be at the same position since the wave function vanishes for ri = rj , si = sj .

3.2

Thomas-Fermi approximation

P |A|P = P AP | = P P A| = |

( semi-classical): Assume each e feels average potential (r) (spherically symmetric) V = Ze2 other electrons e(r) r

2 combinations are important: 1. totally symmetric: | S with P | S = | S Completely symmetric linear combination of all N ! combinations 2. totally anti-symmetric (1)P | A Example N = 3 |
S

Poisson equation: 2 = 4 with r > 0 and the total charge density from other electrons and nucleus: = e(r) + Ze2 (r) Let n be the number of states in a certain energy range: n = 0 if the energy E = n=
2 (2 )3 p2 2m

with

P |

1 = ( (1, 2, 3) + (2, 1, 3) + (1, 3, 2) 3! + (2, 3, 1) + (3, 1, 2) + (3, 2, 1)) 1 = ( (1, 2, 3) + (2, 3, 1) + (3, 1, 2) 3! (2, 3, 1) (3, 2, 1) (1, 3, 2))

e > 0

if E < 0

2me

=
0

8 nd p = (2 )3
3

2me

p2 dp =
0

8 (2me)3/2 3(2 )2

Spin-Statistics Theorem Particles with integer spin (bosons) are described by symmetric wave functions, particles with half-integer spin are called fermions are described by anti-symmetric wave-functions. (Proof needs relativistic QM) Look at N non-interacting identical particles (1 . . . N ) = N i=1 i (i) 6

Plug this into Poisson Equation which leads to a dierential equation for 2 = 32e2 1 d2 r(r) = (2me)3/2 2 r dr 3(2 )3
Ze r

Solve numerically with boundary conditions: (r) r 0 and normalize 4 = (r)r2 dr = Z : R const aZ 1/3

for

3.3

The Harttree approximation

3.4.1

Hartree-Fock approxiamtion 1 (1) . . . ... .. . ... N (1) . . .

Assume (1 . . . N ) = 1 (1) . . . N (N ) as solution to: Improve ansatz for (1 . . . N ) = H (1, . . . , N ) = E (1, . . . , N ) with
N 1 N!

H=
i=1

Ze2 p2 2m ri

+
i>j

e2 |ri rj |

N (1) N (N ) fully compatible with Pauli. As we proceeded with Hartree, plug into Hamiltonian and minimize. We will see that only the potential terms changes: d3 ri
j =i

d3 rj

e-e-interaction

Now let i be distinct and orthogonal (partially taking into account Pauli principle) and normalized. We want to nd stationary states with respect to variation in i taking into account the normalization condition via Lagrange multilpiers i .

e2 |ri rj |

i (ri )j (rj )i (ri )j (rj ) i (ri )j (rj )i (rj )j (ri )

Hartree exchange term

To understand the exchange term, consider N = 2: 1 (1, 2) = (1 (1)2 (2) 1 (2)2 (1)) 2! Write down all terms for the interaction: | H =
i

d3 r i (r) d3 r
i<j

2m

Ze2 r

1 | |ri rj | d3 r1
d3 r2 ( 1 (r1 )2 (r2 )1 (r1 )2 (r2 ) + 1 2

i (r)

+ +
i

d3 r i (r)j (r )

e2 i (r)j (r ) |r r |

1 (r1 )1 (r1 )1 (r2 )2 (r1 ) 1 2)

d3 r|i (r)|2 1
i

3.5

The periodic table and Hunds rules

Take functional derivative

2

A single electron in an atom feels an eective potential Ve (from nucleus and other electrons, still spherically symmetric). i = Rnl(r) Ylm (, )ms where the Rnl is dierent from Hydrogen. General rules: n small, stronger binding l small, electron is closer to the nucleus

2m

Ze2 r d3 r

i + Vi (r)i (r) = i i (r) e |j (r )|2 |r r |

2

Vi (r) =
j =i

where the last term is the interaction of the ith e with the potential caused by all other j = i e and i is the ionization energy of the ith electron. Solve numerically with iterative procedure start with guess (0) (0) for i and plug into potential term to obtain Vi , plug into (0) the Hamiltonian and solve for i .

3.4

Physical interpretation multipliers i

of

Lagrange

Multiply Hamiltonian by i: d3 r 2 |i i |2 2m Ze2 + Vi |i |2 = i ri

For each n: l 0 1 2 3 name S P D F deg 2(2l+1) 2 4 6 10 K-Shell n=1 l=0 2 H,He L-Shell n=2 l=0 2 Li, Be l=1 6 B-Ne M-Shell n=3 l=0 2 Na-Mg l=1 6 Al-Ar N-Shell n=4 l=0 2 n=3 l=2 10 n=4 l=1 6

(1s)2 (2s)2 (2p)6 (3s)2 (3p)6 (4s)2 (3d)1 0 (4p)6

where the i is the ionization energy of the i-th electron, assuming others are not aected.

The conguration of electrons determines the chemical properties of elements. What is the Hunds rules (empirically) [Notation: 2s+1 LJ ] 7

Exanple: Carbon (1s)2 (2s)2 (2p)2 For each of the 2 2p-electrons we can take: ml = 1, 0, 1 ms = 1 2 6 possibilities for both, so in 65 total 2 = 15 possibilities. 0, 2 symmetric 1 anti- symmetric 1 0 symmetric anti- symmetric

Which we plug into the TDSE

0) (0) i c n + En cn |n n

= L= S=
n

cn exp

(0) En t

(0) (0) En |n + m

(0) Vmn (t)|m

Swap labels on m and n on right hand side: i c n exp

n

Total wave function is L S J 2s+1 Lj 1 0 0 0 S0 3 1 1 0 P0 3 1 1 1 P1 3 1 1 2 P2 1 2 0 2 D2

anti-symmetric: deg 1 1 3 5 5 15

i i

(0) (0) En t |n

=
n,m

cm exp

(0) (0) Em t Vnm (t)|n

And we arrive at: c n = (i )1

m eimn t

Vmn exp

(0) (0) (En Em )t cm

1. Make spin maximal spin part more symmetric, orbital part more anti-symmetric electron further away from each other less repulsion (for C, S=1) 2. Make L maximal electrons on average for the away from each other less repulsion (no impact for C) 3. ESO = const(j (j + 1) l(l + 1) s(s + 1)) const> 0 if subshell no more than half lled J = |L S | const< 0 if subshell more than half lled J = |L + S |
j) c( n

where nm = n Now expand in

(0) E (0) Em )

(0) 2 (2) cn = c(0) n + cn + cn +

1 c(1) n = (i ) m

Vnm einm c(0) m

(j 1) Vnm einm cm m

= (i )

Let the system be in state |i (0) tion cm = im :

(0)

at time t0 with intial condi-

Approximation methods for timedependent problems

c f = (i )1 Vf i eif i t cf (t) = (i )
(1) t

(1)

Vf i eif i t dt
t0

We now want to know the time evolution | (t) = U (t, t0 )| (t0 ) We know: i | (t) = H (t)| (t) which results in a more t complicated relation between H and U .

Hence, the transition probability for the system to be found (0) in state |f at time t Pif = |cf |2 = which is valid if |cf |2
(1)

1
2

Vf i eif i t dt
t0

+ O(2 )

4.1

Time-dependent perturbation theory

Let H (t) = H0 + V (t) with a free part H0 which is timeindependent and solvable and a small perturbation V (t). i | (t) ) = H (t)| (t) = (H0 + V (t)) | (t) | (t) =
n

4.2

Constant perturbation

Let V (t) = 0 for t < t0 = 0 and V (t) = V for t > t0 Pif = 1

t 2

cn (t) exp

(0) (0) En t |n

|Vf i |2
t0

eif i t dt f i t 2

(t)| (t) = 1 We can also write

(0) V (t)|n =

|cn |2 = 1
n

2 4 2 (1 cos f i t) = 2 sin2 f i f i sin2 t = 2 t

t

(0) (0) (0) |m n |V (t)|n m Vmn (t)

t () = 8

<

1 2 t

=0

and t () d = 1 with limtinf t () = (). So in the limit we obtain for the transition probability: lim Pif = t
2

such that U satises: i U (t, t0 ) = H (t)U (t, t0 ) with the formal solution: U (t, t0 ) = 1 + 1 i dt H (t )U (t , t0 )
t0 n=0

|Vf i |2

(0) Ef

(0) Ei

f i 2

= (0)

2t

|Vf i |2 (Ef Ei )

(0)

Now solve by iteration: U (t, t0 ) = U (1) |t, t0 = U (2) |t, t0 = = So we arrive at:
t

= 1 + U (0) +

For the transition rate=Probability/time we have f i = 2 |Vf i |2 (Ef Ei )

(0) (0)

1 i 1 i 1 2!i

dt1 H (t1 )
t0 t t2

dt2 H (t2 )
t0 t t0

dt1 H (t1 )

Consider transitions into continuous spectrum (E ) where E2 (E ) dE is the number of states in energy range E1 E2 . E1 Golden Rule: f i
f

dt1 dt2 T (H (t1 )H (t2 ))

t0

(E )f i dE =

(Ef )|Vf i |

U (n) (t, t0 ) = (i )n
t0

tn

t2

dtn H (tn )
t0 t t

dtn1 H (tn1 )
t0 t

dt1 H (t1

1 (i )n n!

dt1
t0 t0

dtn1
t0

dt1 T (H (tn ) . . . H (t1 ))

4.3

Periodic perturbations
it + it

where T is the Time-ordering operator: T (H (tn ) . . . H (t1 )) = H (t (1) ) H (t (n) ) t (1) > t (2) > > t (n) Full solution U (t, t0 ) = T e
i
t t0

Let V (t) = V e +V e for t > t0 = 0 The transition probability Pif is given by Pif = 1
2 t 2

dt
t0

V eit + V + eit

H (t ) dt

=
2 t 2 t t + 2 sin 2 sin 2 (f i ) 2 (f i + ) | V | + | V | f i f i 2 2 2 f i + t t f i 2 2

4.5

The adiabatic approximation

+ Re(Vf i Vf+ i )F (f i , )
2 2 Behavior for t large (t ). Recall that (sin distribution) interference term vanishes. For the transition rate we have:

Here V (t) is not small but changes slowly. ADD PICTURES

if =

2 2 |Vf i |2 (Ef Ei ) + |Vf+ i | (Ef Ei + )

Ef =Ei + Ef =Ei +

Theorem For an adiabatic change Hi Hf , a system that is initially in the n-th eigenstate of Hi will evolve into into the n-th eigenstate of Hf (no level crossings) Proof: Let H (t) = En (t)|n (t) | (t) = cn (t) e(i
n )1
t 0

absorbtion

emmission

4.4

The interaction picture

En ( ) d

Consider again the evolution operator | (t) = U (t, t0 )| (t0 ) with the following properties: 1. U (t, t0 ) 2. U (t, t1 )U (t1 , t0 ) = U (t, t0 ) 3. i | (t) = H (t)| (t) t =i | (t) = t

|n (t)

ein

=
n

cn (t)ein |n (t)

Plug into Schr odinger equation: i

n

n + icn c n |n + cn | n |n

=
n

cn ein H |n

Multiply by m | H (t)U (t, t0 )| (t0 ) 9 n ei(n m ) c m = cn m |

compute

Now for m = n H |n = En |n n |n + H |n = E n |n + En | H n |n = (En Em ) m | m |H Put into equation for c m m c m = cm m |

n=m

m c m (t) = c m m |
t

cm (t) = cm (t0 )eim t Introduce number density

m = i
t0

d m ( )|m ( )

cn

|n m |H ei(n m ) En Em

(r) =
i

(r ri )

only 1e

(r r1 )

small where the last sum is an adiabatic approximation for H 0 and also must not have degeneracy. m c m (t) = cm m |
t

Current desnsity j(r) = then rewrite V (t) = e e2 2 d3 r j(r)A(r, t) + ( r ) A e ( r ) ( r , t ) 2mc2 c

dominant term drop e c2
2

1 2m

(pi (r ri ) + (r ri )pi )
i

cm (t) = cm (t0 )eim (t)

m = i
t0

m ( ) d m ( )|

If the system is in state m at time t, H remains in this state (t) = cm (t)eim (t) |m (t) = eim (t) eim (t) |m (t) where eim (t) is the geometric phase and eim (t) the dynamic phase. (Berry phase)

=0

Write V (t, r) for a single electron in terms of Fouriertransform j(j) = d3 reikr j(r) = pi ikn p e + eikn i 2m 2m

Interaction of matter with classical radiation

So for the potential, we get: e V (t) = (2 )3 c d3 k

=1,2

(k, )j(k)(k, )eik t

Here, radiation is treated as a classical ld

+ (k, )j(k) (k, )eik t which has the form of section 4.3: V ek t + V ek t

5.1

Basics from EM and QM I

External classical eld B = A, E = A (in relativity, , A A ) Physics is invariant under gauge tranformations: A A + A A + (r, t) 1 (r, t) c

5.2

Induced emission and absorption

Consider an atom in an external (classical) EM eld. Compute the transition amplitude/rate of state 0 into n (n = 0). From Section 4.3 for a single mode (k, ) n0 (k, ) = 2 (En E0 )

e2 |(k, )|2 | n |j(k)(k, )|0 |2 c2

|Vm |2

Gauge choice: here Coulomb gauge A = 0 Maxwells Equations in free space wave equation for A: A Solution: A= d k (2 )3
3

For incoherent radiation (no interference eects) n0 = (2 )3 = d3 k

1 2 A = 0 c2 t2

no (k, ) d

(k, )(k, )e

ikrik t

+ (k, ) (k, )e

ikr+ik t

d (2c)3 2 n0 ( c)2 (2c)3

n0 (k, ) | n |j |0 |

where (k, ) are the coecients of linear combinations and {1, 2} is the polarization k = 0 2 polarizations. q q2 p2 H= + V0 + (pA + Ap) + A2 + q 2m 2mc 2mc2
H0 V (t)

The reverse process induced emission 0n = 2e2 n0 ( c)2 (2c)3 | |2 | 0 |j(k) (k)|n |2

10

Aside, there is a third process of spontaneous (without external eld) emission.

5.3

Dipole approximation and selection

where x + iy sin ei r = x iy = sin ei z cos This is most of the time 0 except if n ,l ,ml |z |n,l,ml = 0 if l = l 1, ml = ml n ,l ,ml |x iy |n,l,ml = 0 if l = l 1, ml = ml 1 (Or use Wigner-Eckart theorem with r as vector operator) Hence the selection rules for E 1 transitions (dipole approximation) are l = 1 m = 0, 1

Transition are governed by 0 |j(k) (k)|n j(k) =

1

1 peikk + eikk p 2m
7 1

k for visible light (10 ) r size og atom Bohr radius 1010 m eikr = 1 ik r + (Dipole approximation) Aside: This is equivalent to a term er E = d E with the dipole moment d = er (magnetic moment: B) Proof 1 p2 [rx , H0 ] = rx , 2m 1 = ([rx , p] p + p [rx , p]) 2m with [rx , p] =
y

These rules are notated by beyond-dipole transitions (e.g. E 2 quadrupole transitions.) Further selection rules: S = 0

i xy py

[rx , H0 ] =

px i m p [r, H0 ] = i m e |n 0 | r A c e = i 0 | r A |n c ei (En E0 ) 0 | r A |n = c ei = 0 | [r, H0 ] A |n c

since the spin part of the wave function is not aected by r E. It is always true that there is no transition J = 0 J = 0 (Total angular momentum conservation)

emission 0 | er E |n =

Potential scattering

We consider H = H0 + V (r) with lim|r| |r|V (r)=0 which is (in general) not a Coloumb potential. V is restricted to a small region and we want to nd stationary solutions (r, t) = e
i

Et

(r)

for r

using above Eq. 0 | er E |n = e p e 0 | A |n = 0 | j A |n c m c

Steady incoming beam scattered by the potential (more general treatement in section 7)

Proof 2 Make gauge transformation with (r, t) = A(t) r: A A + = 0 1 1 0= = Ar = E r c c H := e = er E atomic transitions are only possible if n ,l ,ml |r|n,l,ml = 0 given l, ml this imposes constraints on l , ml which leads to selection rules (in dipole approximation) The restrictions can be obtained by looking at properties of spherical harmonics: x + iy ml d Yl (, ) x iy Ylml (, ) z 11

6.1

Elastic Scattering and cross-sections

we are looking for solutions to (H0 + V ) | = E | Ein = Eout = of the form r k (r) in (r) + sc (r) = eikr + f (, ) eikr r
2 2 p2 k = 2m 2m

where we are not interested in (r) for small r (in range of ikr V ) and f (, ) is the scattering amplitude and e r is the outgoing spherical wave Dierential cross section d N = d F

N : #particles scattered into d per time in N d F : ux of incoming particles, number/time/unit area Exercise: For |in |2 = 1 (1 part/volume), F =V = outgoing: j = ... = k er f (, ) |2 2 m r p k = m m

Put everything into () for r l 1 Al sin(kr + l ) kr 2 l eikr 1 = (2l + 1)il sin(kr ) + fk kr 2 r Al ikr i l il Al ikr i l eil e e 2e e e 2 2i 2i l l 1 1 (2l + 1)il eikr ei 2 (2l + 1)il eikr ei 2 + kfl eikr 2i 2i Finally fl = 2l + 1 2il 2l + 1 il (e 1) = e sin(l ) 2ik k

total cross section

d = |f (, i) |2 d d d d

Full Information on f (), thus

6.2

Partial-wave analysis
k eikr + f ()
r

f ( ) =
l=0

2l + 1 il e sin(l ) Pl (cos ) k
fl

eikr r

Total Cross Section tot = d

1

(*) Central Potential

d|f ()|2

k = fk =

Rl (kr)Pl (cos )
l=0

2
1

dcos
l=0 l =0

fl fl Pl (cos )Pl (cos )

fk (k )Pl (cos )
l=0

Use

dcos Pl (cos )Pl (cos ) =

2 2l+1 ll

Schr odinger equation for Rl solutions l l Rl (kr) Bl sin(kr ) + Cl cos(kr ) 2 2 1 l = Al sin(kr + l (k )) kr 2

r

tot =
l=0

1 kr

2l + 1 sin2 (l ) k2

l
l=0

6.2.1

The Optical Theorem

For V=0, we have Cl = 0, i.e l = 0. Next nd a relation between phase shifts l (k ) and scattering amplitude f () . Aside: Free particle eigenfunctions in spherical coordinates: Elmk (r, , ) = cjl (kr)Ylml (, )|E =

Im(f ( = 0)) = Im
l=0

fl

= Im
l=0

2l + 1 il e sin l k

=
2 k2 2m

l=0

2l + 1 sin2 (l ) k

form a basis, expand eikr = eikr cos in this basis:

l

It follows tot = 4 Im(f ( = 0)) k

eikr =
l=0 ml =l

Clml Jl (kr)Ylml (, ) al jl (kr)Pl (cos )

l=0

Often an easy way to compute the total cross section by computing Im of forward scattering amplitude.

x coecients al (use orthogonality)

Partial-wave useful if not too many l contribute. (2l + 1)i jl (kr)Pl (cos )
l

ikr

=
l=0

L = l = bP 12

6.3

Coulomb scattering

In QM the particles are undistinguishable when idential. Two pictures with a particle A and B going to each other. Moreover: Total wave function (spin+space+. . . ) must be either symmetric or antisymmetric under exchange A B , r r. Spatial wave function sym/antysym = eikr eikr + (f () f ( )) eikr r

So far we have assumed rV (r) 0, |r| , but this is not the case for Coulomb scattering. However, exact solution is known (recall Hydrogen atom)
2

2m

Z1 Z2 e2 r

(r) = E (r)

hydrogen E < 0 (bound states),

r

lim | (r)| = 0

scattering E > 0 with dierent 1 4 ( + ) + 2 = + 2

2

Example: Coulomb scattering of two protons (spin 1 2 , fermions t.w.f. antisymmetric). Let us look at unpolarized protons and assume that the potential does not depend on spin. Spin wave function: prob prob.
1 4 3 4

singlet state (anti sym.) triplet states (sym.)

Spatial wave function prob

1 4

: do not contribute Conuent hypogeometric equation 2 linearly independent solutions: nd the linear combination which is regular at the origin. Result for r mZ1 Z2 e2 = 2k
z (r ) ei(kz+ log 2k(rz))

symm. sing = |f () + fc ( )|2

prob

3 4

antisym. trp = |fc () fc ( )|2

k=ke

Unpolarized cross-section: )e
i(kr log 2kr )

distorted plane wave

2k sin2

(1 + ) i log(sin e (1 i )

2 2

distorted outgoing plane wave

3 1 |fc () + f ( )|2 + |fc () fc ( )|2 4 4 1 = |fc ()|2 + |fc ( )|2 (fc ()fc ( ) + fc ()fc ( )) 2
Z1 =Z2 =1

This looks the same as (r) = e

ikr

eikr + f ( ) r
r

e 4E

1 1 + 4 sin 2 cos4
classical

cos log tan2 sin2

2

cos2

but gets additional phases, because not rV (r) Crosssection d = |fc ()| = 2 4 d 4k sin
2

Mott scattering formula

Z1 Z2 e2 4E

1 sin4

6.4
2

LippmanSchwinger Greens function

equation

&

Rutherford scattering formula (classical!) Phases drop out in this case Additional phases can have an eect in scattering of 2 idenA B tical particles. Here 2 2, . Go to the center of mass frame (sec 2.1)
2

Again: Ek =
2

k 2m

2 2

2m

2 + Ek k (r) = V (r) (r)

2 + V (r) (r) = E (r)

If we know the Greens function dened by

2

2m = m1 m2 m = m1 + m2 2 reduced mass

2 + Ek gk (r) = (r)

then we can write a formual solution for k (r) k (r) = eikr + d3 r gk (r r )V (r )k (r )

V interaction potential r = rA rB relative coordinate 13

with eikr solution to homogeneous equation (V = 0) Checik it at home.

Idea: As in section 4.4 we can turn this formal solution into a series for k (in powers of V ) First: Compute gk : Go to Fourier space gk (r) = We get
2

for both points inside:

+ gk (r) + gk (r)

Both points outside 0

+ gk outgoing spherical wave gk incoming spherical wave

d3 q (2 )

3e

iqr

gk (q)

2m

2 + Ek gk (r) =

d3 q (2 )
3

2m

q2 +
iqr

2m

k 2 eiqr gk (q)

+ What we need is gk !

= (r) =

d q (2 )

3e

k (r) = eikr

d3 r

m eik|rr | V (r ) (r ) 2 2 |r r |

Check asymptotic behaviour (r V (r ) 0) gk (q) =

3

2m
2

k2

1 = q2
1

Ek

q 2m

2 2

1 |r|

|r r | r 1 gk (r) = 1 (2 ) 2m
2 0 2

dq
0

| d
1

dcos q 2

2m
2

k2

= = :

1 (2 )
2 2

2m
2

1 (2 )
2 0

dq

q2 1 eiqr eiqr We get: 2 iqr k q 2

1 eiqr cos q2

r r cos + O r r rr = r er r =r r

m 2 2

1 ir

dq

q eiqr k2 q2

k (r) = eikr

m 2 2

d3 r

eikre

iker r

V (r )k (r )

dq
0

q 1

6.5
dq

The Born Approximation

Formal solution: k (r) = eikr + G+ k (r r ) = Es folgt f = m 2 d3 r eiker V (r )k (r) d3 rG+ k (r r )V (r)k (r)

Integral is not well dened! We need a prescription for the poles. We use contour integral, close it in upper half plane q = qR + iq
m

eiqr = eiqR r eq m r

m eik|rr | 2 2 |r r |

Solve this perturbatively by iteration

q +k

k (r) = eikr +
n=1

d3 rKn (r, r )eikr

with the Kernel We deform the contour at q = k dierent options, giving dierent asympt behaviours for gk (r)! For negative point outside and positive point inside curve: K1 (r, r ) =G+ k (r r )V (r) . . . K1 (r, r ) =
+ gk (r) = 2i

V1

d3 r K1 (r, )Kn1 (r , r)

Vn

m 2 2

1 q m e Resq=k eiqr = ir (q k ) (q + k ) 2 2 r

ikr

For negative point inside and positive point outside curve: m eikr 2 2 r

aaly leading to:

n

=
gk (r ) =

d3 ri
i=1 G+ k (r2

+ G+ k (r rn )V (rn )Gk (rn rn1 )

r1 )V (r1 )

14

Retaining the rst term we obtain the rst Born approximation k (r) = eikz m 2 2 d3 r V (r )eik(ez er )r e
f (1) (,)
ikr r

General scattering theory

General scattering more complicated than in section 6 e.g. production of new particles. Want to use general representation, so | is a general state in Hilbert space (not nec. wave function)

(Assume k along the z-Axis) f (i) is the Fourier Transformation of the potential with respect to q. q k (ez er ) = k k momentum transfer

7.1

Dynamics of scattering

Start from time dependent Schr odinger

q = 2k sin 2 Central Potential V (r ) m f (, ) = 2 2 m 2 sin(qr ) r 2 dr = 2 qr

(i) 1

i t |, t = H |, t H = H0 + V r dr V (r )e
2 iqr cos

d
1

dcos

... = ... (i t H0 ) |, t = V |, t = |, t Green operation G0 (t, t ) through (i t H0 ) G0 (t, t ) = (t t ) 1 ( operators)

and we nally arrive at: f (1) () = q = 2k sin 2 2m 2q dr r V (r ) sin(qr )

inhomogeneous dierential equation in t Solutions i i H0 (tt ) G+ 0 (t, t ) = (t t ) e G 0 (t, t ) = + sodass i t G+ 0 (t t ) i

Note: f (1) is real! Compare optical theorem Example: Yukawa Potential V (r) = V0 er r

where is the range of interaction. f

(1)

2m () = 2 V0 q

dr e
0

sin(qr ) =

2m
2

V0 2 + q 2

=i

t (t t ) e
i

H0 (tt

q 2 +q 2

= (t t ) e

H0 (tt

) + (t t ) i H e i H0 (tt ) 0

For the cross section follows: d d

(1)

= (t t ) + H0 G+ 0 (t t )
2

= |f (1) ()|2 =

2mV0
2

1 (2 + 2k 2 (1 cos ))2

Note: The superscripts are related to those in section 6

pm G 0 (t, t ) = G0 (t t )

and for the total cross section:

(1) tot 1

= 2
1

dcos 2mV0
2 2

2mV0
2

Write solution to Schr odinger 1 (2 + 2k 2 (1 cos ))2 | , t = | 0 , t +

dt G 0 (t t ) V | , t

= 2

2 + 4k 2 2

with | 0 , t solution to homogeneous problem

Take the limit 0 which means an innite range of interaction: V (r) = d d V0 r

(1) Coul

(i t H0 ) |0 , t = 0 The physical solution is given by | + , t , since G+ (t t ) moves forward in time. (retardation) To make connection with section 6: t E

Coulomb = 2mV0
2 2

1 (2k 2 (1 cos ))2

but the total cross section diverges! Note limr rV (r) = 0 for Coulomb.

G+ 0 (E ) = 15

dt e

Et

G+ 0 (t) =

i
0

dt e

Et i H0 t

with
+ G+ 0 (t) = G0 (t, t = 0)

Consider again
0 | = | + E H0 + O+ 0 = | + 1 1 V |

for t need E E + i0 , 0 > 0 G 0 = 1 E H0 i0+ E H0 i0+

0 T | E E i0+

1=

0 0 d | |

| , t evolves with H , but was equal to free state | 0 , t @ t Let be a complete set of quantum number of H0 (including E )
0 | , t | ,t

0 T V

Transfer matrix This state satises: d e or

i

f ()|

d e

0 f ()|

make Fourier t E of Eq. dt e

i

Et

| ,t

dt e

Et

0 | ,t

d f ()|

iH 0

0 d f ()|

| (E ) |

0 (E ) | 0 |

dt e

Et

dt G 0 (t t ) V | , t tt+t

| = lim e+

H i H0

0 0 | = |

with Mller operators Typical scattering experiment: At t prepare state with quantum number of H0

dt e

Et

+ G+ 0 (t) = G0 (E )

V | (E ) =

dt e

Et

V (E )

Q: What is amplitude for this state to end up in (another) eigenstate of H0 with quantum number . A:
+ 0 =

0 | = | + G0 V |

0 0 0 S +

(Lippmann-Schwinger)

S =Scattering operator, with S = lim e

i

Solution:
| = 1 G 0V 1 0 | =

H0

H (0 ) i H0 0

1
1 G 0

V 1 0 E?a H0 i0+ V + V | = E H0 i0+ V 1 0 = E H + V i0+ | E H i0+

G E 0 = 1 + G V |

(Gpm 0 )

0 |

= ex 1: sheet 6: i

lim U (, 0 ) = U (, )

i i i d U (, 0 ) = e H0 (H H0 ) e H (0 ) e H0 0 d i i = e H0 V e H0 U (, 0 ) = V ( )U (, 0 )

V ( )

V ( ) evolution operator in IA picture section 4.4. Solution U (, 0 ) = T e and S = U (, ) =1 i

2 i
V 0

0 = 1 + G V |

( ) d

can also be obtained from (exercise 2) | , t = lim i G+ (t t ) |0 , t

t

dt1 V (t1 ) +

t1

dt1

dt2 V (t1 )V (t2 )

7.2

Mller operators & scattering operator

+ ... Note: SS = 1 S operator is unitary

: Complete set of quantum numbers

0 0 H0 | = E | H | = E |

S -matrix 16
0 0 S S =

option 1 1st term:

insert S operator

which can be interpreted as an harmonic oscillator. (a a + aa ) with the states Recall QMI: H = 2 |0 a|0 = 0 (a )n |0 n! a = n + 1|n + 1 N |n = n|n

0 0 1 = ( )

|n 2nd term i i
0 e dt1
i

H0 t

V e

H0 t

N = a a

dte

(E E )t

0 0 V

To motivate the interpretation of A as collection of independent harmonic oscillators compute H= 1 d3 r(E2 + B2 ) 1 E= A c d3 k i i = eikrik t eikrik t (2 )3 c c

= 2i (E E ) V 3rd and 4th exercise sheet 8

0 0 0 | = | + G 0 (E )V | = | + G (E )V | 0 + 0 S = S =

For the E-Field we get: d3 rE2 = d3 r d3 k (2 )3 d3 k (2 )3 i c i c

7.3

Structure of the S-Matrix

eikrik t eikrik t
+ 0 | | = (g (E ) g 1 (E ))V | + 0 | | = |V (g + (E ) g (E ) ,

+ eik rik t eik rik t = GAP d3 k (2 )3 Dene a (k, ) = such that we obtain und p= d3 k (2 )3 ka kl akl

S =

+ 0 | + |V

= ( ) +

1 1 + | E h + iO+ E H iO+ 1 1 0 + |V | E E + iO+ E E iO+

=2i (E E )

d3 r

it( ) ir(kk ) e e c2

2iO + lim0+ 0 (E E )2 +(O + )2

So we obtain
0 + S = ( ) 2i (E E ) |V | T

(k, ) 2c

with the transition matrix T .

8
8.1

Quantization of radiation elds

Quantization of free radiation elds

Second quantization: So far for A classical eld: a() =function a(k, ) a(k, ) Operator a(k, ) a(k, ) Operator A, H, P A, H, P Commutation Relations:
[ak , ak ] = [a k , ak ] = 0 3 [ak , a k ] = (2 ) (k k )

From Section 5.1 we have the solution of the MaxwellEquations: A(r, t) = d3 k (2 )3 ()(k)eikrik t

+ () (k)eikr+ik t with = c|k|, the sum being over the polarization and the polarization vector k (k) = 0 Consider the time dependence of a single mode (k, ): qk = (k, )ek t
2 q k = k qk

k: continuous label, discrete Another way to quantise the eld A L= 17 1 1 F F = (E2 B2 ) 16 8

Dene the conjugate momentm eld = Then A, A, L 1 = = E A 4c

General d3 k (2 )3
m

ak |n1 , . . . , nm

=
i=1

ni |n1 , ni1 , , nm

[Ai (x, t), Aj (x, t)] = [ i (x, t), i (y, t)] = 0 [Ai (x, t), Aj (y, t)] i (x y)ij Concerning : Actually i d3 k (2 )3 ki kj ij 2 k
tr eik(xy) i ij (x y)

Compute Expectation value of H in state |n1 (k1 , 1 ) |n1 = n1 |H d3 k (2 )3 a ak + 2 k ak a k

a k ak + (0)

|n1

1 (innite) constant ground state. The (0) corresponds to 2

Now A, H, are operators. What is the Hilbert space?

n1 |H |n1 = =

d3 k (2 )3

a k ak 1 n1

8.2

Fock Space
Hence

n1 |ak |n1

Built up as for single harmonic oscillators with ladder operators. a (k, ) = a k is the creation and a(k, ) = ak the annihilation operator. Start with vacuum state |0 dened by ak |0 = 0 Then |1(k, ) a k |0 is a state with one photon having momentum k and Polarization . General State |n1 (k1 , 1 ), . . . , nm (km , m ) = Note: |n1 (k1 , 1 ), . . . , nj (kj , j ), . . . , nm (km , m ) = Then d3 k (2 )3 1 n1 ! nj + 1|n1 , nj + 1, , nm
n1 nm (a (a k1 ,1 ) km ,m ) |0 n1 ! nm !

n1 nm |H |n1 |nm =
i=1

i n i

Introduce Interaction with matter (Compare Section 5)

2 q q2 (pA + Ap) + A 2mc 2mc2 in Coulomb gauge A = 0 pA = Ap:

V =

q2 2 q pA + A 2 mc 2mc is an operator in Fock space and will be used to compute transition matrix elements V =
0 0 V = |V |

8.3
ak |n1 (k1 , 1 ) d k (2 )3
3

Photon emission and absorption

We have considered these processes before in section 5.2

n1 ak (a k1 ,1 ) |0

H = Hc + Hem + V Hc = Hem = V 1 8 p2 i 2m d3 r(E + B )

2 2

Using the commutation relations:

n1 1 (a n1 [ak , a k1 1 ) k1 1 ] + (ak1 ,1 )ak

Interaction matter-photons

= n1 (2 ) (k k1 )1 + we get n1 = (a )n1 1 |0 n1 ! k1 1 = = n1

(a k1 ,1 )ak

Eigenstates | 0 =|matter |photons =|A; n1 (k1 , 1 ), . . . , nm (km , Absorption of a photon V = B ; (n 1)(k, )|V |A; n(k, ) = = 18 e mc e m d3 k (2 )3

(n1 1)! (ak1 1 )n1 1 |0 n1 ! (n1 1)!

2 c2 B ; (n 1)(k, )|a(k )p(k , )eik

n1 |(n1 1)(k1 , 1 )

2 n B ; |p (k, )eikr |A n

Emission of a photon V = B ; (n + 1)(k, )|V |A; n(k, ) e = m 2 n + 1 B ; |p (k, )eikr |A n + 1 (classical electron radius)

mc

2 2 = r0

Remark This is non-zero even for n = 0, spontaneous emission Recall classical: (absorption) Tn0 = T =0n (emission) nk Tn0 = nk Now: T +1 0n

However, there are further contributions of order 2 e4 golden rule (sec 4.2/4.3) Transition rate 2 |T |2 cross section
d d

(nal photon). . .

8.5

2nd order contribution

8.4

Scattering of photons by atoms

for T Feynman diagrams

2 t1

Involves creation and annihilation of photon. needs a (kf , f )a(ki , i ) Recall V =

2 e2 e pA+ A 2 mc 2mc

S = . . . V V In our case i
2

dt1

dt2

t1 (E E ) i t2 (E E )

First-Order-Contribution V = F ; 1(kf , f )| e = 2mc2

2 (1) 2 e A |I, 1(ki , i ) 2mc2 2 c2 d3 k (2 )3 ikrt 2

t1

dt1

i

dt2 e mc
2

dN e d3 k (2 )
3

(EN EF )ti

e )

(EI EN )t2

d3 k (2 )

ikr+it1

F, P (f , f )| ak p k eikrit1 +ak pk e

|N

F ; 1(kf , f )|(ae (a e =
ik r t

+a e

ikr+t

+a e

ik r+ t

)|I ; 1(ki , i )

ik j r+i t2 N | ak p k eik ri t2 + a |I, 1 (ki , i ) k p k e

e2 2 c2 2 F |(ki , i ) (kf , f )eit(i f ) eik(ki kf ) |I need 1 a (ki , i ) and one a (kf , f ) 2 2mc i f = . . . = F | a kf . . . |N N | . . . aki |I + F | aki . . . |N N | . . . a f |I
k

Recall from section 7.2 H = H0 + V S = ( ) i

Kramers Heisenberg formula i

R

dt1 e

t1 (E E )

0 0 V

dt1 e

t1 (EI + i EF f )

2e2 F | . . . |F m i f

d = d +

mc

f |i f F I + i

F | p f |N
N

N | p i |I

golden rule (sec 4.2/4.3) Transition rate 2 |T |2 cross section d d (nal photon energy f + a ( f )) divide by ux v = c (section 6.1) nr. states d3 k (2 )
3

F | p i |N N | p f |I | m (EI f EN )

limiting cases Rayleight scattering elastic scattering

k 2 dk d (2 )
3

2 f d

(2 ) c3
2 f d

d( f )

|I = |F i = f EI EN

(f ) =

(2 ) c3

combine i f with other terms 1 I | x i , p f |I i

N | p f |I I | p f |N

2 f d 1 2 e4 f 2 ir(ki kf ) = | T | = |i |I |2 f F|e 3 d c m2 c4 i (2 ) c3 (f )

I | i f |I = = 19 1 i

I | x i |N
N

N | p f |I

 put everything together: 1 1 ( ) + = 2 + 2 + ... EN EI EI EN + (EI EN ) (EI EN ) d 2 ( ) | = r0 d m2

4 2

Solution: (t, x) = Arikxit (x) = Aek x k = ,k x

I | p f |N
N

N | p i |I
2

(EI EN )

+ |2

k 2 = k k =

m2 c2 2 2 k = 2 c2

2 r0 classical e-radius, 4 blue sky red sunset

which leads to possibly negative energy solutions: = m2 c4 + p2 c2

Thomson scattering i EN EI scattering o free elec-

(large compared to bindig energy trons)

In analogy to the Schr odinger equation try to dene a probability density (x, t) and probability current density j(x, t) satisfying: + j = 0 t j= ( () ( )) 2mi i = 2mc2 t t

d = r2 |i f |2 d for unpolarized photons 1 2 a i (ki , i ) f

i f a b ki ki a (kf , f ) b i f a b kf kf ab 2 kf b

In the covariant form this becomes: j = (c, j) = i ( ( )) 2m

1 = 2 with

ab

ki

1 = 1 + cos2 2

Note: (x, t) is not positive denite and hence cannot be interpretes as a probability density. = (ki , kf )

9.2
=
2 dcos 2r0

Dirac Equation

8 2 r 1 + cos2 = 3 0

, ) equation. Most general linear equatiTry a linear (in t on: i = H = i c + mc2 t i ci i + mc2

Resonances

What if EN EI + i
N

so far : neglected nite lifetime of EN , N = time evolution

EN t N t

= e

t(EN iN )

where = (1 , 2 , 3 ) and are four non-commuting coecients. Iterate this equation: c2

2

with N that one cannot neglect 1 EI EN + iN 1 (EI EN ) + 2 N

2

2 = i ci i + = mc2 t2
2

i cj j + mc2

(i j + j i )i j i (i + i )i mc2 + 2 m2 c4

|T |2 |

|2 =

and compare to the Klein-Gordon-Equation It follows that

2

9
9.1

Relativistic Quantum Mechanics

Klein-Gordon equation
+ mc2
2

2 = t2

c2 i j + m2 c4

2 = 1 (i + i ) = {i , } = 0 (i j + j i ) = {i , j } = 2ij From anticommutation realtions we see that the coecients cannot be numbers

=0

1 , c t

20

(Exercise: dimension four matrices are the simplest possibilities) wave function: = (1 , 2 , 3 , 4 )T an a possible choice for und are i = 0 i i 0 =

such that the new equation holds and where S () is a 4 4 matrix. Start from S ()Dirac equation S () i mc (x) x x = S () i mc (x) x x
1 = i S () () S () (x) S (x )

12
0

0 1 2

= diag(1, 1, 1, 1)

= S ()(i mc)

which is called the Dirac representation No Rewrite the Dirac equation in terms of -matrices: , 0 {0, 1, 2, 3} i = i

Compare with the dirac equation in S :

1 S () () = S

0 =

12
0

12

i =

0 i

i 0

or
1 () S () = S

Note: We can use any other representation = U U Take times the Dirac-equation = i ci i + mc2 i t 0 = i c i i + mc2 i t which can be written more compact as: (i mc) = 0 Notation any 4-vector: a = a (i mc1) = 0

A proper Lorentz transformation has 6 parameters (3 rotation and 4 boost parameters) = (anti-symmetric). LT:
= g g

Claim: For an innitesimal proper Lorentz transformation i S () = 11 2

1 with = 2 [ , or for nite Lorentz transformation

S () = e 2 (Compare to QM I rotations) For parity (t, x) (t, x) or 1 1 = 0 we get for = 0S 0 S = 0 = iS i S = i

The adjoint Dirac equation

l l 0 0 0 = i ( )) = (i 0 0 mc)

0 1 1

(i mc)) = 0 (i + mc) = 0 = 0 is the dirac adjoint where satises: The current ) + = 0 j = ( j 0 = 0 0 =

S () = 0 Phase Dene 5 = i0 1 2 3 in Dirac representation 5 = Note that (5 )2 = 1 0 1 1 0

9.3

Covariance of the Dirac equation

Consider the Lorentz tranformation:

x = x = x =

x x x

Now we can parametrize any 4 4 matrix in terms of the following 16 matrices: {1, 5 , , 5 , } We know (x) S () (x)
LT (x) (x)S 1 () LT

For the Dirac equation (i mc) (x) = 0 (i mc) (x ) = 0 requires transformation (x) (x) = S () (x) 21

Bilinear Covariant
Scalar
pLT (x) (x) 1 S = (x) (x) S

Some properties of u and v u (p, ri )u(p, rj ) = u (p, ri ) 0 u(p, rj ) cp 1 0 =( E+ i ) i, 2 0 1 E + mc cp i j = (E + mc2 )i j E + mc2 = 2mc2 i j mc2 = 2mc2 ij Similar v (p, ri )v (p, rj ) = 2mc2 ij and v u = u v = 0. E + mc2 j cp j E +mc2

(x) (x) = (x) (x)

0 0

P arity

Pseudo scalar
pLT (x)5 (x) 1 5 S = (x) 5 (x) S P arity (x) (x) 0 5 0 = (x)5 (x)

Vector Axial vector 5 det() 5 Rank 2 tensor

(Convention: in some books ) We can also show

2

u v

u 1 , 2mc2 v

u,v form a basis.

u(p, ri ) u(p, rj ) = c( p + mc)

i=1

which is the projection on the positive energy states. = v (p, ri ) v (p, ri ) = c( p + mc)

9.4

Solution of the Dirac equation

(x) = (1 , 2 , 3 , 4 )T (1)

Show equivalence for complete set u(p, rj ) and v (p, rj ), e.g.

2

u(p, ri ) u(p, ri ) u(p, rj ) = 2mc2 u(p, rj )

i=1

4 Componentes (22) - Spin and pos/neg energy. Go to momentum space: + (x) = eikx u(k ) (x) = e+ikx v (k ) positive Energy negative Energy

c( p + mc)u(p, rj ) = c( p mc + 2mc)u(p, rj ) = 2mc2 u(p, rj ) Note: Same as

2

kx = k x = t k x, write this as + (x) = e (x) = e+

i

(k, )( (k, )) 0 = g +
=1

k k k2

(Etpx)

u(p)

positive Energy negative Energy E p = ( , p) c

(Etpx)

v (p)

9.5

Interpretation of Solutions
1 2

Now we show that the Dirac Equation descibres spin H = p + mc2 = ijk l [xj , pl ]pk = i ijk j pk Since [L, h] = i p = 0 L is not conserved. However, J = L + S must be conservede S = 0. We need to nd S such that [J, H ] = 0, i.e. [S, H ] = i p L=xp

Dirac: We obtain the following matrix equation: ( p mc)u(p) = 0 ( p mc)v (p) = 0 mc p p E c mc Pich normalization vector E + mc2 E + mc2 r u(p, r) = cp r E +mc2 ( p mc) = v (p, r) =
cp E +mc2 E c

[Li , H ] = [ijk xj pk , l pl ]

=0

E+

mc2

r r

with 1 = (1, 0)T , 2 = (1, 0)T 22 and of course [Si , Sj ] = i ijk Sk

Claim: S= 2 = i 1 2 3 = 2 2 0 0

P P commutes with all generators, P 2 is Lorentz-invariant (Casimir operator). What else do we need to know? Consider any p : Little group of p : subgroup of all Poincare transformations that leave p invariant. For p in rest frame p = (m, 0, 0, 0) the little groups are just the rotations. 2 2 Let p = L q , i.e. for any q with q = m > 0 we can nd a Lorentz transformation L, such that p = L(p)q is in rest frame. States in Hilbert space are related: |p = U (L(p))|q Under any LT : |p U ()|p = U ()U (L(p))|q U (L(p))U 1 (L(p))U ()U (L(p))|q U (L(p))U (L1 (p))U ()U (L(p))|q U (L(p))U (L1 (p)L(p))|q
rotation

Proof: [Si , Sj ] = i ijk Sk is obviuous. [Si , H ] = [ use 1 2 3 = i [1 2 3 i , H ] 2

1 jkl j k l 3!

i 1 j k n n [ , p + mc2 ] 2 2

j k use 1 2 3 i = 1 2 ijk

i 1 j k n [ { , } {j , n } k ]pn 2 2
2 kn 2 jn

i = ijk (j pk k pj ) 2 = i ( p)i Lets look at relation between spin and coordinate transformation more carefully: QM I(Section 10.4): Generators of rotations and Translations J i , P i [P i , P j ] = 0 [J , J ] = i [J , P ] = i
i j i j ijk

It is a rotation since p p q q (for q = (m, 0, 0, 0)) this must be a rotation) Additional labels in |p, s are aected by rotations only:
L(p)

ijk

Pk

|p, s U ()|p, s = U (L(p))Dss |q, s Second Casimir Operator W W = m2

2

= Dss |p, s

Coordinate transformation: x x = Rx + a a state | under a certain representation | | = U (R, a)| in a relative boosts
x = x + a

s(s + 1)

which is called Pauli-Lubanski vector (axial) 1 W = J P 2 is rest frame P = (m, 0, 0, 0) and W = (0, w) [Ki , Kj ] = i ijk Jk [Ki , Kj ] = i ijk Kk 1 m wi = i J P = i J = mJi 2 2 One can classify states according to m2 , s. ( Note: in general we can have m2 = 0, or m2 < 0)

with generator J = J0i = Ji0 = Ki Jij = Jji = iijk Jk

9.6

The non-relativistic limit

Lie algebra of generators [P , P ] = 0 [J , J ] = i (g J g J g J + g J ) [P , J ] = i (g P g P ) under Lorentz transformation a state |p transforms under a certain representation |p |p = U ()|p 23

p| v of Dirac equation. We will deConsider expansion in |m rive the Hamiltonian used in section 2(for ne structure) The Dirac equation in presence of the EM-eld is e p p + A c

Write = (, )T , where the entries are two-component spinors. (p+ e A mc) c = =0

E c

+e (p + e c mc c A) e e p + c A) ( E c + c mc)

where E e e + mc = p + A c c c e E e p + A = + mc + c c c = p+ e cA
E c

Repeat = eiS with S =

i O 2mc2

which leads to

H + Heven + O With the third and last iteration = eiS we arrive at H O2 O4 +E 2mc2 8m3 c6 1 [O, [O, E ]] i [O, O] +O 2 4 2 4 8m c 8m c m3 = H = mc2 + S = i O 2mc2

+ mc + e c

p+ e cA 2mc

such that e e e 1 E + mc = p + A p + A c c c c 2mc 2 e e 1 p + A + i(i ) A + A = 2mc c c [A 1 e = 2m p + c A

2

e 2 B e = (E mc ) = E 2mc

First term: O2 1 e e = i (pi + Ai )j (pj + Aj ) 2mc2 2m c c 2 e 1 e p+ A + Bi j = 2m c 2m 1 1 = {i , j } + [i , j ] 2 2 = ij + iijk k Second term: p4 O4 = + . . . (relativistic Correction to kinetic Energy) 3 6 8m c 8m3 c2

where for , compare to section 2.3: e e H B= gs B = gB g = 2 2m 4m

p| Lets do this more systematically (expan in |m ). iS Find a transformation = e (Foldy-Wouthuysentransformation) such that odd operators(mixes and )

are suppresed by

|p| m

e 0 = c p + A c Schr odinger equation: i = i t eiS = i [t eiS ] + eiS i t t = i [t eiS eiS + eiS HeiS

Third term: =H 1 ( ) [O, [O, E ]] = i i 2 4 8m c 8m2 c2 = (i )e [i i , j Ej ] 8m2 c2

2 2

[j j , eV ]
j e(j V V j )=j e[j ,V ]

where i2 i3 H = H + i[S, H ] + [S, [S, H ]] + 2! 3! 2 i i ] ] S [S, S [S, [S, S 2 3! Recall H = mc2 + O + (even: = e) and set S= Compute i[S, H ]: i[S, H ] = i[ i O, mc2 + O + ] 2mc2 i O 2mc2

where = i j i Ej j i Ej i = E + i ( E) E i (E ) = [, E 2i (E ) + i ( E) such that we have = ie 2 4m2 c2 (E ) ( E) 2 e [ E] 8m2 c2

2

= [O, ] 2mc2 [ O, O] = OO O O = 2 O2 e [ O, ] = c[ , ] p + A = 2O c O2 O4 [O, [O, E ]] +E 2mc2 8m3 c6 8m2 c4 3 i [O, O] O i O + [O , E ] + 2 4 2 2 2 8m c 2mc 2mc 2mc
O

ADD MISSING

H = mc2 +

10

Second Quantization

24

Classical eld theory quantized eld theory done always for radiation elds (Section 5 to 8)

10.1

Creation and annihilation operators for bosons and fermions

Field operator: ( x) = ai i (x),

(x)a i (x)

Bosons: recall radiation elds ak , a k now i {k, }, (discrete)

[ai , aj ] = [a i , aj ] = 0

Acting on the vacuum state as: (x) =

j

|j j |
i

a i i (x)|0

[ai , a j] States

= ij

=
ij

|j 0|aj a i |0 i (x) |j 0|[aj a i ] ai aj |0 i (x) ij |j 0|ij |0 i ( x) ij

n1 , n2 , . . . , nm | =

n1 (a i)

n1 m (a m)

= |0 = =
i

n 1 ! . . . nm !

For the case if fermions the commutators become anticommutators [, ] [, ] {bi , b h } = ij {bi , bj } =
2 (b i) = 0 {b i , bj }

|i i (x) =

|i i|x = |x

{, } [, ]+

(x) creates a particle localized at x (x) annihilates a particle localized at x Commutation relation: b i |1 = and
(b i ) |0

ni = {0, 1} Pauli for part. i: |1 = b i,

b 1 b2 |0 b 2 b1 |0

[ (x), (y )] = [ (x), (y )] = 0 =0
i (x)j (y )[ai , a j] ij i (x)i (y ) = (x y) i

|n1 = 1, . . . , n2 = 1 = anti-symmetric Orthogonality

= |n2 = 1, n1 = 1

[ (x), (y )] = =

n1 , . . . , nm |n1 , . . . , nm = n,n . . . nm ,nm Completeness

1

Many-particle states |n1 . . . nm n1 . . . nm | = 1 1 |x1 , x2 , . . . , xn = (x1 ) . . . (xn )|0 n! Example: Two identical bosons/fermions at x1 and x2 1 ij (x1 , x2 ) = x1 , x2 , ij = 0| (x2 ) (x1 )a i aj |0 2 1 = 0|am an a i aj |0 m (x2 )n (x1 ) 2 nm
ni mj mi nj

ni =0

Counting operator n=
i

ni =
i

b i bi

10.2

Field operators

Let i (x) a wave function (coordinate representation of a state) with basis

d3 xi (x)j (x) = ij

where we have + for bosons and - for fermions. 1 = (j (x2 )i (x1 ) i (x2 )j (xi )) 2 for xed number n of particles, Hilbert space Hn :

i (x) = x|i

(We can think of i as eigenfunctions of H, Hi = Ei ) Consider any state f (x) L2 : f (x) =

i

: Hn Hn+1 : Hn Hn1

ci i (x), d3 yi (y ) f (y )

ci = =

and the Fock space dened as the direct sum d3 yf (y )

i (3) (xy) (y )i (x) i

F= 25
n=0

Hn = H0 H 1 H 2

10.3

Obersvables in second Quantization

Consider commutation relations between eld operators (x), (y ) = (x y )

!

Oberservable are expressed in terms of elds operators in F. Example particle number density: QM: probabilty density (x) = | (x)|2 . Now: (x) = (x) (x) =
ij a i aj i (x)j (x)

d3 k (2 )3

d3 k ikx ik x e e [ak , a k ] (2 )3

Time dependende of eld operators: Schr odinger Picture Heisenberg (x, t) = e

i

Ht

(x)e

Ht

=
ij

T =

d3 x (x)

2 2 2m

(x)

i (x, t) = [H, (x, t)] = e Ht t

momemtum representation (x) =

i

ai i (x) (x) =
ai i (x) (x) = i

d3 k ak eikx (2 )3 d3 k ikx a e (2 )3 k

Take the case of a free boson H = T :

(x) =

[T , (x)] = Now

d3 y

2m

y (y )y (y ), (x)

such that T becomes T = d3 x

3

d3 k (2 )3

d3 k eix(kk ) a k ak (2 )3 3
(2 ) (kk )

2 (ik )2 2m

y (y )y (y ), (x) (x)y (y )y (y ) = (x) (y ) (x)y (y )y (y ) = [ , (x)] + (x) (y ) (y ) (x)y (y )y (y )

(xy )

k a ak (2 )3 k
Nk

Potential U ( x) = Then U= = d3 x (x)U (x) (x) k1 (2 )3 k1 (2 )3

3 3

d3 q iqx e U (x) (2 )3 = = d3 xeik1 k2 eik2 k2 eik1 q a k1 ak2

(2 )3 (k1 k2 q)

d3 y
2

2 y (x y) (y ) 2m

k2 (2 )3
3

g (2 )3

2m

2 x (x)

In the free case we have i

2 (x, t) = 2 (x, t) t 2m

k2 a ak U (k1 k2 ) (2 )3 k1 2

V =
4

d3 x1 d3 ki (2 )3 i=1

d3 x2 (x1 ) (x2 )V (x1 x2 ) (x1 ) (x2 ) d3 q (2 )3 d3 x1 eix1 (k1 k3 q)

(2 )3 (k1 k2 q)

plus additional interaction terms (in QFT)

10.4

Quantization of relativistic edls

d3 x2 eix2 (k2 k4 +q) a k1 ak2 ak3 ak4 V (q) (2 )3 (k2 k4 +q)

Start with a Lagrangian density L for a classical eld theory Compute conjugate momentum eld 26 Impose equal-time (anti-)commutation relation

k1 (2 )3

k2 (2 )3

q a ak q ak4 +q V (q) (2 )3 k2 3

Example 1: Free Scalar Field (x, t) = (x) 1 1 m2 c2 2 V () 2 2 2

=:m2 V =0

Proof d4 k 2 (k 2 m2 )(k0 ) (2 )4 d4 k 2 2 = (k0 k )(k0 ) (2 )3 d4 k 1 = ( (k0 k ) (k0 + )) (k0 ) (2 )3 2k d3 k 1 = (2 )3 2k Now express ak and a k in terms of and

L=

The resulting action is S= such that S = 0 L L =0 ( ) dt d3 xL = d4 xL(, )

d3 xexx k (x, t) + i (x, t) = ak eik t ak = ak = d3 xeikx k + i d3 xeikx k i

and we obtain the Klein-Gordon-Equation for our L: m2 = 0 Conjugate momentum eld (x, t) = L (x, t) =

Check Consistency [ak , a k ] = = d3 x d3 yeik tikx eik t+ik y k + i, k i

Hamiltonian H= = 1 2 L= d3 x L d3 x

d3 xex(kk ) ei(k k ) (k + k ) (x y)
(2 )3 (kk )

= (2 )3 2k (k k )

d3 x 2 + ()2 + m2 2 ak a k
a k ak + (0)

Second Quantaziation We promote (x) (x) and (x) (x) to operators and impose the following equal time(!) commutation relations: (x, t), (y, t) = [ (x, t), (y, t)] = 0 (x, t), (y, t) = i (x y) where we used commutators (not anti-commutators) since we have a spin 0 bosonic eld. Now as for radiation eld (x, t) = k 1 ikx+ik ak eikxik + a ke (2 )3 2k k 2 + m2 .
3

H = =

1 2

d3 k 1 a ak + (2 )3 2k k

where the (0) corresponds the an innite ground state energy. Normal Ordering:, denoted by : :: anti-commute all a to the left of a : H := subtracted 0|H |0 =
1 Example: spin 2 -eld ( = 1, c = 1)

k 1 a ak k (2 )3 2k k

where ak is an operator in Fock space F and k := (x, t) = (x, t) =

3

L L L =0 ( ) (i ) = m (i + m) = 0 =

(x)(i m) (x) =

k 1 ikx+ik ik ak eikxik + ik a ke (2 )3 k

Field momeentum conjugate to Note: By the change in normalization d k (2 )3

3

d k 1 (2 )3 k

= Hamiltonian H= 27

L 0 = i = i

the right expression becomes Lorentz-invariant.

L = d3 x

d3 xi

Again, second quantization and imposing of commutation relations: { (x, t), (y, t)} = { (x, t), (y, t)} = 0 { (x, t), (y, t)} = i (x y) where , {1, 2, 3, 4} are the spinor indices. (In the case of fermions use {, } = [, ]+ ) Field operators in momentum representation (x, t) =

Change the integration variable in the second term from k k = d3 k ((k0 0 k + m)0 + (k0 0 k m)0 ) (2 )3 2k
(2k0 (0 )2 ) =2k

k 2k eik(xy) = (x y) (2 )3 2k

k 1 (2 )3 2k

for the Hamiltonian: x b(k, r)u (k, r)eikx + d (k, r)v (k, r)It eikfollows H= :H: d3 k k (2 )3 2k d3 k k (2 )3 2k
b kr bkr dkr dkr r b kr bkr + dkr dkr r

r =1

Remark:b creates E > 0 electron, while d creates an E > 0 positron. This eld satises the Dirac equation since ( k m)u = 0 ( k m)v = 0 The anti-commutation relations of the elds are consistent with
3 {bkr , b k r } = {dkr , dk r } = (2 ) wk rr (k k )

and the charge 0 : Q :=: j :=:

3

=:

k
k r

= {b, b} = {d , d } = {b, d} = = 0 Consequently

{ (x, t), (y, t)} 3

(2 )3 2

b kr bkr dkr dkr

k
k rr

(2 )3 2k

(2 )3 2

all this? - Add interactions: ikx ik y {bkr , b e Why k r }u (k, r )u (k , r )e

+{d kr , dk r
3

}v (k, r)v (k

, r )eikx eik y

p p + eA i +e A (i + m) + eA L=
eA j

= k (2 )3 2k
r

u(k, r)0 ) eik(xy) (u(k, r)

((k+m)0 )

(v (k, r) v (k, r)0 ) eik(xy)

((k+m)0 )

Recall U = T ()

28