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D. Rubin

December 2, 2010

Lecture 32-41

November 10- December 3, 2010

1 Stationary state perturbation theory

1.1 Nondegenerate Formalism

We have a Hamiltonian

H = H

0

+ V

and we suppose that we have determined the complete set of solutions to H

0

with

ket [ n

0

` so that H

0

[ n

0

` = E

0

n

[ n

0

`. And we suppose that there is no degeneracy.

The eigenkets of H satisfy

H[ n` = E

n

[ n` →(H

0

+ V )[ n` = (E

0

n

+ ∆

n

)[ n` (1)

(E

0

n

−H

0

)[ n` = (V −∆

n

)[ n` (2)

where E

n

= E

0

n

+∆

n

. We multiply the perturbative term by a real parameter λ and

insist that ∆

n

is analytic in λ as λ goes from 0 to 1. Then Equation 2 becomes

(E

0

n

−H

0

)[ n` = (λV −∆

n

)[ n` (3)

The perturbation is small if the energy shift is small compared to the spacing of the

unperturbed levels that might be connected by the perturbation. That last equation

is our Schrodinger equation and we could invert it like so

[ n` =

1

E

0

n

−H

0

(λV −∆

n

)[ n`

1

To make sure we don’t do something crazy like divide by zero we project out the

[ n

0

` ket by introducing a projection operator

φ =

¸

k=n

[ k

0

`'k

0

[

Then we make the equation safe from nan.

[ n` =

φ

E

0

n

−H

0

(λV −∆

n

)[ n`

We are not losing anything here since Equation 3 says that

'n

0

[ λV −∆

n

[ n` = 0 (4)

Finally, so we have something sensible as λ → 0 we add the solution to the unper-

turbed part and write

[ n` = [ n

0

` +

φ

E

0

n

−H

0

(λV −∆

n

)[ n`

One last thing to note. Normalization. It seems that 'n [ n

0

` = 1. We will use this

fact. [ n` is not normalized by itself. Now Equation 4 says that

∆

n

= λ'n

0

[ V [ n`

Now we suppose that

[ n` = [ n

0

` + λ[ n

1

` + λ

2

[ n

2

` + . . .

and

∆

n

= λ∆

1

n

+ λ

2

∆

2

n

+ . . .

Then equation powers of λ. Our energy equation becomes

λ∆

1

n

+ λ

2

∆

2

n

+ . . . = λ'n

0

[V

[ n

0

` + λ[ n

1

` + λ

2

[ n

2

` + . . .

So

∆

1

n

= 'n

0

[ V [ n

0

`

∆

2

n

= 'n

0

[ V [ n

1

`

∆

3

n

= 'n

0

[ V [ n

2

`

2

And for the wave function

[ n

0

`+λ[ n

1

`+λ

2

[ n

2

`+. . . = [ n

0

`+

φ

E

0

n

−H

0

(λV −(λ∆

1

n

−λ

2

∆

2

n

+. . .))[ n

0

`+λ[ n

1

`+λ

2

[ n

2

`+. . .

Equating stuﬀ linear in λ we get

[ n

1

` =

φ

E

0

n

−H

0

V [ n

0

` (5)

Next everything quadratic in λ gives

[ n

2

` =

φ

E

0

n

−H

0

V [ n

1

` −∆

1

n

[ n

1

`

[ n

2

` =

φ

E

0

n

−H

0

V

φ

E

0

n

−H

0

V [ n

0

` −'n

0

[ V [ n

0

`

φ

E

0

n

−H

0

V [ n

0

`

**And we can use our solution for [ n
**

1

` to see that

∆

2

n

= 'n

0

[V

φ

E

0

n

−H

0

V [ n

0

` =

¸

k=n

[ 'n

0

[ V [ k

0

` [

2

E

0

n

−E

0

k

It is evident that degeneracy could get us in trouble.

1.2 Examples

1.2.1 Helium

To ﬁrst approximation, the energy of the ground state of helium is

2Z

2

E

0

= −2Z

2

e

2

2a

**= 2(4)(−13.6ev) = −108.8ev
**

The next approximation would be to include the interaction of the electrons as a

perturbation.

V =

e

2

[r

1

−r

2

[

The unperturbed wave function is taken to be

ψ(r

1

, r

2

) = ψ

0

(r

1

)ψ

0

(r

2

) =

8

πa

3

e

−2(r

1

+r

2

)/a

3

where

a =

¯ hc

αmc

2

Set the polar axis along r

1

and

E

1

= e

2

8

πa

3

2

e

−4(r

1

+r

2

)/a

r

2

1

+ r

2

2

−2r

1

r

2

cos θ

2

r

2

1

dΩ

1

r

2

2

dΩ

2

= e

2

5

4a

Then the total energy is

E = 2(4)

−e

2

2a

+

5e

2

4a

= −

11e

2

4a

= −

11

2

(13.6ev) = −74.8ev

1.2.2 Stark eﬀect for rigid rotator

The hamilonian for the rigid rotator is

H =

L

2

2I

where I is the moment of inertia and the vibrational levels are assumed inﬁnitely far

apart as compared to the spacing of the rotational levels. Then the energy eigenstates

and eigenvalues are [ ψ` = [ l, m` and E

l

=

¯h

2

l(l+1)

2I

. In the presence of a uniform

electric ﬁeld in the z direction we introduce

V = −ezc = −erc cos θ

We suppose that e'r` = d is the electric dipole moment of the rotator. (All states

have the same radial wave function). We can write

V = T

1

0

= −dc

4π

3

Y

1,0

(θ)

We need to evaluate

l

2

, m

2

[ T

1

0

[ l

1

, m

1

**The matrix element is non zero if m
**

1

= m

2

and ([l

2

− l

1

[ ≤ 1, (Wigner Eckart),

l

1

= l

2

, (parity). Then the non zero matrix element can be written

l ±1, m [ T

1

0

[ l, m

= −dc

4π

3

Y

∗

l±1,m

Y

1,0

Y

l,m

dΩ

4

= −dc

4π

3

(2(1) + 1)(2l + 1)

4π(2(l ±1) + 1)

'1, 0, l, m [ l ±1, m`'1, 0, l, 0 [ l ±1, 0`

= −dc

(2l + 1)

(2(l ±1) + 1)

'1, 0, l, m [ l ±1, m`'1, 0, l, 0 [ l ±1, 0`

= −dc

l

2

−m

2

4l

2

−1

The unperturbed levels are all degenerate. But since H

0

and V both commute

with L

z

, there is no mixing, and non degenerate theory is OK. In each of the m

supspaces, the spectrum is non degenerate. The ﬁrst order correction is zero, by the

rules above, ('l, m [ T

1

0

[ l, m` = 0. The second order correction reduces to the two

terms corresponding to l = ±1. Finally

lm

2

=

dc

E

0

l

2

l(l + 1) −3m

2

2(2l −1)(2l + 3)

The degeneracy is only partly removed, since it depends on m

2

. Some symmetry

remains. We could compute the electric dipole moment.

µ ∼ e 'n [ z [ n`

We have that

[ n` ∼ [ n

0

` +

¸

k=n

'k

0

[ T

1

0

[ n

0

`

E

0

n

−E

0

k

[ k

0

`

Then

µ ∼

¸

k=n

'n

0

[ z [ k

0

` 'k

0

[ T

1

0

[ n

0

`

(E

0

n

−E

0

k

)

=

1

c

¸

k=n

'n

0

[ T

1

0

[ k

0

` 'k

0

[ T

1

0

[ n

0

`

(E

0

n

−E

0

k

)

1.2.3 Stark eﬀect in hydrogen

As in the case of the rigid rotator, the perturbation commutes with L

z

so there is

no mixing of states with diﬀerent m and we use non degenerate perturbation theory.

Also, since all of the eigenstates with deﬁnite angular momentum have deﬁnite parity,

there is no ﬁrst order correction. Another way to see this is to note that although

the perturbed Hamiltonian does not commute with L

2

, it does commute with L

z

.

So there is no change to the z-component and therefore no mixing of states with

5

m = m

**. Parity eigenstates have zero electric dipole moment. The electric dipole
**

moment is

d = 'α, l, m [ x [ α, l, m` =

x[ψ(x)[

2

d

3

x = 0

since x has odd parity. An electric dipole emerges in second order since the ﬁrst

order correction to the wave function includes contributions of opposite parity. That

also means that the electric dipole moment scales with the applied electric ﬁeld. The

energy shift is quadratic in E

The polarizability is α where

∆ = −

1

2

α[E[

2

The energy shift is second order

∆

2

= e

2

c

2

¸

k=0

[ 'k

0

[ z [ 1, 0, 0` [

2

(E

0

0

−E

0

k

)

We approximate the sum by assuming that the denominator is constant, (this will

give us an upper limit on the energy shift) and noting that

¸

k=0

[

k

0

[ z [ 1, 0, 0

[

2

=

¸

all k

[

k

0

[ z [ 1, 0, 0

**since '1, 0, 0 [ z [ 1, 0, 0` = 0. The sum over all k becomes
**

¸

all k

[

k

0

[ z [ 1, 0, 0

=

1, 0, 0 [ z

2

[ 1, 0, 0

=

1

3

'r

2

` = a

2

0

Therefore,

∆

2

≤ e

2

c

2

a

2

0

(E

0

0

−E

0

k

)

= ∆

2

≤ e

2

c

2

a

2

0

(−e

2

/2a

0

−

−1

4

e

2

/2a

0

)

= −c

2

8a

3

0

3

2 Degenerate perturbation theory

Our formalism falls apart if there are degeneracies. But actually, it is OK as long as

the perturbation does not couple the degenerate states. If it does couple degenerate

states we are in trouble since then we have ﬁnite numerator and an energy denomina-

tor that is zero in Equation 5. The strategy is to ﬁnd a new basis for the degenerate

states in which none of the states in that basis are coupled by the perturbation.

6

2.1 Formalism

So here’s what we do. Suppose that there is a degenerate set of states and we are

interested in the eﬀect on the perturbation of states at that energy. The states

are [ i`, i = 1, 2, 3 for example. Now if 'i [ V [ j` = [V [δ

ij

then we do not have a

problem. Business as usual. If there are oﬀ-diagonal terms, then we need to ﬁnd

a diﬀerent linear combination of the degenerate states for which the perturbation

matrix is diagonal. That is we diagonalize

V =

¸

¸

'1 [ V [ 1` '1 [ V [ 2` '1 [ V [ 3`

'2 [ V [ 1` '2 [ V [ 2` '2 [ V [ 3`

'3 [ V [ 1` '3 [ V [ 2` '3 [ V [ 3`

¸

→

¸

¸

'I [ V [ I` 0 0

0 'II [ V [ II` 0

0 0 'III [ V [ III`

¸

**The new basis is related to the old by a unitary transformation.
**

[ I` = a[ 1` + b[ 2` + c[ 3`

The states [ I`, [ II`, [ III` are the eigenkets of the perturbation matrix and the

diagonal elements of the perturbation matrix in the new basis are the eigenvalues.

In fact we see that the eigenvalues are the ﬁrst order energy shift. The ﬁrst order

shift in the state vector is given as before by

[ n

1

` =

¸

k=D

'k

0

[ V [ n

0

`

(E

0

n

−E

0

k

)

[ k

0

`

The states in the degenerate subspace do not contribute because all of the oﬀ diagonal

matrix elements are zero. Likewise for the second order correction to the energy.

2.1.1 Projection operators

We could more formally use the projection operator approach. We go back to the

Schrodinger equation

0 = (E −H

0

−λV )[ l`

= (E −E

D

−λV )P

0

[ l` + (E −H

0

−λV )P

1

[ l`

Projecting from the left by P

0

and P

1

we get

P

0

((E −E

D

−λV )P

0

[ l` + (E −H

0

−λV )P

1

[ l`)

= (E −E

D

−λP

0

V P

0

[ l` −λP

0

V P

1

[ l` (6)

P

1

((E −E

D

−λV )P

0

[ l` + (E −H

0

−λV )P

1

[ l`)

= −λP

1

V P

0

[ l` + (E −H

0

−λP

1

V P

1

)[ l` (7)

7

We solve Equation 7 for [ l` and then project out the states not part of the degenerate

subspace and then the denominator is safe

P

1

[ l` = P

1

1

E −H

0

−λP

1

V P

1

λP

1

V P

0

[ l`

∼ P

1

[ l

1

` ∼

¸

k=D

[ k

0

`

'k

0

[ V [ l

0

`

E

0

D

−E

0

k

(8)

Then substitute Equation 8 into Equation 6 for P

1

[ l` multiply by P

0

and we have

(E −E

D

−λP

0

V P

0

−λP

0

V P

1

1

E −H

0

−λP

1

V P

1

λP

1

V )P

0

[ l`

∼ (E −E

D

−λP

0

V P

0

)[ l` = 0

The energies are the eigenvalues of the perturbation matrix. In summary we divide

the space into the subspace of degenerate states, and the all the rest. The exact

state vector is a linear combination of all [ l

0

` kets.

[ l` =

¸

a

i

[ l

i

`

Then the Schrodinger equation including the perturbation is

(E

0

l

−H

0

)[ l` = (λV −∆

n

)[ l` (9)

Substitute the expansion for ∆

l

and

[ l` = [ l

0

` + λ[ l

1

` + λ

2

[ l

2

` + . . . .

Here

[ l

0

` =

¸

i=D

a

i

[ i`

[ l

0

` is a normalized linear combination of the degenerate states in the basis in which

the perturbation matrix is diagonalized. Multiply by 'm

0

[ from the left

m

0

[ E

0

n

−H

0

[ l

= λ'm

0

[ V [ l` −∆

l

'm

0

[ l`

and keep the ﬁrst order in λ, when m

0

= l

D

and we get that

0 = 'l

D

[ V [ l

0

` −∆

1

l

'l

D

[ l` →'l

D

[ V `l

D

= ∆

i

D

When m

0

= l

D

(E

0

n

−E

0

m

)'m

0

[ l` = λ'm

0

[ V [ l` −∆

l

'm

0

[ l`

8

To ﬁrst order in λ we have

(E

0

n

−E

0

m

)

m

0

[ l

1

= 'm

0

[ V [ l

0

`

and

m

0

[ l

1

∼

'm

0

[ V [ l

0

`

E

0

l

−E

0

m

and

[ l

1

` =

¸

l=D

'm

0

[ V [ l

0

`

E

0

n

−E

0

m

[ m

0

`

Note that we can always add states with eigenvalue E

0

l

. The above gives no infor-

mation about them. We deﬁne [ l

1

` and all higher order contributions to include no

[ l

0

` or for that matter any of the [ l

D

` degenerate states. Then the exact solution is

[ l` =

¸

i=D

a

i

[ i` +[ l

1

` +[ l

2

` + . . .

and

[ l

0

` =

¸

i=D

a

i

[ i`

'l

0

[ l

j

` = 0, for j = 0. We suppose that the a

i

are chosen so that [ l

0

` is normalized.

We see that in this way [ l` is a solution to Equation 9 independent of the coeﬃcients

a

i

. And the second order energy shift

∆

2

l

=

l

0

[ V [ n

1

=

2.1.2 Second order degenerate perturbation theory

Another strategy

1

for getting second order correction of degenerate states is to write

the true state

[ a` =

¸

α

c

α

[ α` +

¸

µ

d

µ

[ µ`

where the sum over α includes the degenerate states and the sum over µ is all the

others. We know that

(H −E

a

)[ a` = (H

0

+ λH

1

−E

a

)[ a` = 0

1

Gottfried and Yan

9

Then

0 =

¸

α

c

α

(H −E

a

)[ α` +

¸

µ

d

µ

(H −E

a

)[ µ`

0 =

¸

α

c

α

(E

α

−E

a

+ λH

1

)[ α` +

¸

µ

d

µ

(E

µ

−E

a

+ λH

1

)[ µ`

Then multiply from the left ﬁrst by 'β [ which is an element of the degenerate space

and then by 'ν [ which is outside of the degenerate space.

0 = c

β

(E

β

−E

a

) + λ

¸

α

c

α

'β [ H

1

[ α` + λ

¸

µ

d

µ

'β [ H

1

[ µ` (10)

0 =

¸

α

c

α

λ'ν [ H

1

[ α` + d

ν

(E

ν

−E

α

) + λ

¸

µ

d

µ

'ν [ H

1

[ µ` (11)

Drop the last term in Equation 11 as it is higher order in λ. Justiﬁcation for this step

is that the state [ a` is mostly a linear combination of the states in the degenerate

space. The coeﬃcients d

µ

would all be zero in the λ → 0 limit so they are at most

ﬁrst order in λ. Then that last term is second order in λ. You might then argue

that we should drop the last term in Equation 10, but probably 'β [ H

1

[ µ` is more

important that 'ν [ H

1

[ µ` since it connects to the relevant states. Finally, we could

keep the last term in Equation 11, solve for d

ν

, substitute into Equation 10 and then

drop the highest order term. That would be equivalent to solving for

d

ν

= −λ

¸

α

c

α

'ν [ H

1

[ α`

(E

ν

−E

D

)

(12)

Substitution into 10 gives

0 = c

β

(E

β

−E

α

) +

¸

α

c

α

λ'β [ H

1

[ α` + λ

2

¸

µ

'µ [ H

1

[ α` 'β [ H

1

[ µ`

E

µ

−E

D

(13)

which is the eigenvalue problem in the subspace D for the eﬀective Hamiltonian H

eff

'β [ H

eff

[ α` = λ'β [ H

1

[ α` + λ

2

¸

µ

'β [ H

1

[ µ` 'µ [ H

1

[ α`

E

D

−E

µ

.

So we diagonalize 'β [ H

1

[ α`.

Deﬁne P to be the projection operator onto the degenerate subspace T, P =

¸

α

[ α`'α [. Then we can write

H

eff

= λPH

1

P + λ

2

PH

1

1 −P

E −H

0

H

1

P

10

2.1.3 Example

Suppose we have a system with 3 states. The ﬁrst two are degenerate. The third is

at energy ∆ above the two.

H

1

=

¸

¸

0 0 λM

0 0 λM

λM λM ∆

¸

The

H

eff

= −

(λM)

2

∆

1 1

1 1

**The energies and eigenstates are
**

E

S

= −2

(λM)

2

∆

, [ E

S

` =

1

√

2

([ 1` +[ 2`)

and

E

A

= 0, [ E

S

` =

1

√

2

([ 1` −[ 2`)

That’s what happens if ∆ λM. On the other hand, if ∆ ∼ λM, then we treat all

three states as though they were degenerate. Assume the unperturbed energies are

all the same. Then the shift in the energy of each of the three states is given by the

eigenvalues of H

1

which are, E

0

= 0, E

±

=

1

2

(∆±

∆

2

+ 8(λM)

2

). The eigenvectors

are

[ 0` =

1

√

2

([ 1` −[ 2`), [ ±` =

([ 1` +[ 2` +

E

±

λM

[ 3`)

2 + E

2

±

/λ

2

M

2

What if we went back to the weak perturbation case where M <∆, but we had

started with states [ S` =

1

√

2

([ 1` +[ 2`) and [ A` =

1

√

2

([ 1` −[ 2`) and [ III` = [ 3`.

Then

V =

¸

¸

0 0

√

2M

0 0 0

√

2M 0 ∆

¸

Now

H

eff

=

−2M

2

/∆ 0

0 0

11

2.2 Fine Structure

2.2.1 Spin orbit coupling

The magnetic ﬁeld at the electron due to its motion through the E ﬁeld of the nucleus

is

B = −

v E

c

The electric ﬁeld is radial so E =

|E|

r

r and p = mv and then

B =

r p

mc

[E[

r

=

L

mc

[E[

r

Next, note that E =

1

e

∇V =

1

e

∂V

∂r

and we get that

B =

L

mec

1

r

∂V

∂r

The magnetic moment of the electron is

µ

e

= −

e

mc

S

Finally

∆H = −µ B =

1

m

2

c

2

r

∂V

∂r

L S

and if V = e/r then

∆H =

e

2

L S

m

2

c

2

r

3

→

e

2

L S

2m

2

c

2

r

3

Then a factor of

1

2

for the Thomas Precession. The best way to do this is to take the

nonrelativistic limit of the Dirac equation with a vector potential.

Or we could use the Biot Savart Law which states that

B =

(JdV )r

c[r[

3

For a current loop, we ﬁnd the magnetic ﬁeld at the center is

B =

I

cr

3

eλdlv r = −

er p

cmr

3

The unperturbed states have orbital angular momentum and spin. We can use

[ l, m

l

`[ s, m

s

` as base kets with eigenvalues l, m, s, and m

s

, or we can take the linear

12

combinations that would be eigenkets of j, j

z

, l, s. Since L S =

1

2

(J

2

−L

2

−S

2

), it

is clear that it will be more convenient to use the latter. Then

E

1

n

=

e

2

¯ h

2

4m

2

c

2

'

1

r

3

`

j(j + 1) −l(l + 1) −

3

4

E

SO

=

¯ h

2

e

2

4m

2

c

2

1

n

3

a

3

0

[j(j + 1) −l(l + 1) −3/4]

l(l +

1

2

)(l + 1)

¸

where

'

1

r

3

` =

1

n

3

a

3

0

l(l + 1/2)(l + 1)

For j = l ±

1

2

E

SO

=

¯ h

2

e

2

4m

2

c

2

1

a

3

0

n

3

¸

l

−(l + 1)

l(l +

1

2

)(l + 1)

=

mc

2

α

4

4

¸

l

−(l + 1)

n

3

l(l +

1

2

)(l + 1)

**We remember that
**

E

0

= −

1

2

α

2

mc

2

= −

e

2

2a

0

→a

0

=

e

2

α

2

mc

2

=

¯ h

2

me

2

Substitution into the above gives

E

1

n

∼

e

2

¯ h

2

(α

2

mc

2

)

3

2m

2

c

2

e

6

=

¯ h

2

c

2

2e

4

(α

2

mc

2

)

3

(mc

2

)

2

=

1

2

α

2

mc

2

(α

2

)

j(j + 1) −l(l + 1) −

3

4

No dependence on m

l

. No mixing of levels. No need for degenerate formalism. Each

level is split into j = l ±

1

2

.

2.2.2 Relativistic correction

Really

K =

(mc

2

)

2

+ (pc)

2

−mc

2

∼

p

2

2m

−

p

4

8m

3

c

2

13

And

ψ [

p

4

2m

[ ψ

¸

=

p

2

2m

ψ [

p

2

2m

ψ

¸

= '(E

0

−V )ψ [ (E

0

−V )ψ`

=

ψ [ (E

2

0

−2E

0

V + V

2

[ ψ

**We use the fact that p
**

2

is Hermitian in the ﬁrst step.

∆E

1

0

∼ −

(2m)

2

8m

3

c

2

'(E

n

−V (r))

2

` ∼

4m

2

8m

3

c

2

E

2

n

−2E

n

'

−e

2

r

` +'

e

4

r

2

`

∼ −

4m

2

8m

3

c

2

E

2

n

−2E

n

−e

2

n

2

a

0

+

e

4

(l +

1

2

)n

3

a

3

0

∼ −

4m

2

8m

3

c

2

E

2

n

1 −4 +

4n

(l +

1

2

)

∼ −

1

2mc

2

E

2

n

−3 +

4n

(l +

1

2

)

∼ −

1

2

mc

2

α

4

4n

4

−3 +

4n

(l +

1

2

)

∼ −

5

2mc

2

E

0

(

1

2

α

2

mc

2

) =

5

4

E

0

α

2

(Note that

1, 0, 0 [

1

r

[ 1, 0, 0

=

1

a

0

and

1, 0, 0 [

1

r

2

[ 1, 0, 0

=

2

a

2

0

.) Depends on n, l,

not on j. Again there is no mixing of degenerate levels. In general

'

1

r

` =

1

n

2

a

0

, '

1

r

2

` =

1

(l +

1

2

)n

3

a

2

0

2.2.3 Darwin term

The particle cannot be localized to better than its Compton wavelength ¯ h/mc. The

potential that is relevant is not V (r) but some smeared average about the point r.

V (r) = V (r) +

¸

i

∂V

∂r

i

δr

i

+

1

2!

¸

i

¸

j

∂

2

V

∂r

i

∂r

j

δr

i

δr

j

+O(δr

3

)

= V (r) +

1

6

(δr)

2

∇

2

V +O(δr

3

)

14

If δr ∼ ¯ h/mc then

H

D

∼

2

3

π

e

2

¯ h

2

m

2

c

2

δ

3

(r)

Note that according to Merzbacher (p. 206 and 208)

ψ

n,l,m

(0) =

1

(na)

3

n!

2n(n −1)!

=

1

2(na

0

)

3

Then

'n00 [ H

D

[ n00` =

2

3

π

e

2

¯ h

2

m

2

c

2

1

2(na

0

)

3

=

2π

3

e

2

¯ h

2

m

2

c

2

1

2n

3

m

3

e

6

¯ h

6

=

2π

3

1

2n

3

mc

2

α

4

and it exactly compensates for the l = 0 term that we got from the spin orbit term.

Or it would if we did it properly using the Dirac equation.

2.2.4 Fine Structure

Combining all order α

2

corrections we have

E

SO

=

E

2

n

mc

2

n[j(j + 1) −l(l + 1) −3/4]

l(l +

1

2

)(l + 1)

¸

The relativistic correction is

E

1

r

= −

E

2

n

2mc

2

¸

4n

l +

1

2

−3

¸

The total α

2

correction is

−

E

1

n

2

¸

1 +

α

2

n

2

n

j +

1

2

−

3

4

¸

2.3 Stark eﬀect

To determine the eﬀect of an external uniform electric ﬁeld on a set of degenerate

levels we need to exercise a bit more care. Consider n = 2 in hydrogen. There are

2l +1 = 3 levels with l = 1 and 1 level with l = 0. Spin is not relevant. The candidate

15

set of base states are the orbital angular momentum kets. The perturbation matrix

elements 'i [ V [ j`, where V = −ez[E[ are

V =

¸

¸

¸

¸

0 '2, 0, 0 [ V [ 2, 1, 0` 0 0

'2, 1, 0 [ V [ 2, 0, 0` 0 0 0

0 0 0 0

0 0 0 0

¸

Only the upper left is relevant. All of the other states are not coupled. The eigen-

vectors of the upper left 2X2 matrix are

∆

1

±

= −±e[E[ '2, 0 [ r [ 2, 1` '2, 0, 0 [ cos θ [ 2, 1, 0` = ±3ea

0

[E[

The eigenvectors are

[ ±` =

1

√

2

([ 2, 0, 0` ±[ 2, 1, 0`)

These two states are shifted positively and negatively with an electric ﬁeld. The

other 2 states are not eﬀected by the E-ﬁeld.

2.4 Zeeman eﬀect

H =

p

2

2m

+ V

c

(r) −

e

2mc

[B[L

z

+

e

2

8mc

2

[B[

2

(x

2

+ y

2

)

We have

H

Z

= −

e

2mc

[B[(L

z

+ 2S

z

)

and then

H

spin

= −µ B = −

e

mc

S B = −

e

mc

[B[S

z

and

H

spin−orbit

=

1

2m

2

c

2

1

r

dV (r)

dr

L S

Assuming B is very weak so that the spin-orbit piece dominates, we need to evaluate

'j, m, l, s [ L

z

+ 2S

z

[ j, m, l, s` = 'j, m, l, s [ J

z

+ S

z

[ j, m, l, s` Since

[ l ±

1

2

, m` = ±

l ±m +

1

2

2l + 1

[ l, m−

1

2

`[

1

2

,

1

2

` +

l ∓m +

1

2

2l + 1

[ l, m +

1

2

`[

1

2

, −

1

2

`

we can compute

l ±

1

2

, m [ S

z

[ l ±

1

2

, m

= ±

m¯ h

2l + 1

16

Meanwhile

l ±

1

2

, m [ J

z

[ l ±

1

2

, m

= ¯ hm. Then

∆

1

B

= −

e¯ hB

2mc

m

1 ±

1

2l + 1

**2.4.1 Paschen-Back limit
**

If the magnetic ﬁeld is very strong, then total angular momentum is not conserved.

(There is an external torque). But the L

z

and S

z

are ﬁxed. So now it is better to

use the basis [ , m

l

`[ s, m

s

`. It is easy to evaluate 'L

z

+ 2S

z

` but not quite as simple

to compute 'L S` for the spin orbit coupling. But if we write

'L S` = 'L

z

S

z

+

1

2

(L

+

S

−

+ L

−

S

+

)`

and note that 'L

±

` = 'S

±

` = 0 then we get that

'L S` = ¯ h

2

m

l

m

2

2.4.2 Intermediate ﬁeld

Let’s examine the eﬀect of an external magnetic ﬁeld on the n = 2 states of hydrogen.

And we suppose that 'H

spin−orbit

` ≈ 'H

z

`. Now we have to exercise some care in

computing energy shifts. There are 8 degenerate states. We can choose as a basis

eigenstates of j, j

z

, l, s, (l = 1, j = ±3/2, ±1/2,or l = 0, j = ±

1

2

or eigenstates of

l, m

l

, s, m

s

, (l = 1, m

l

= ±1, 0, m

s

= ±1/2, l = 0, m

s

= ±1/2). We have to construct

the perturbation matrix elements 'i [ V [ j` in whatever basis we have chosen and

V = −

e

2mc

B(L

z

+ 2S

z

) +

e

2

2m

2

c

2

1

r

3

L S

Let’s pick the basis of eigenstates of j, j

z

, l, s. Then the L S term only contributes

along the diagonal. So let’s look at the eﬀect of the external ﬁeld. We had better

label the states.

[ 1` = [

1

2

, −

1

2

, 0,

1

2

` = [ 0, 0`[

1

2

, −

1

2

`

[ 2` = [

1

2

,

1

2

, 0,

1

2

` = [ 0, 0`[

1

2

,

1

2

`

[ 3` = [

1

2

, −

1

2

, 1,

1

2

` =

1

3

[ 1, 0`[

1

2

, −

1

2

` −

2

3

[ 1, −1`[

1

2

,

1

2

`

17

[ 4` = [

1

2

,

1

2

, 1,

1

2

` = −

1

3

[ 1, 0`[

1

2

,

1

2

` +

2

3

[ 1, 1`[

1

2

, −

1

2

`

[ 5` = [

3

2

, −

1

2

, 1,

1

2

` =

2

3

[ 1, 0`[

1

2

, −

1

2

` +

1

3

[ 1, −1`[

1

2

,

1

2

`

[ 6` = [

3

2

,

1

2

, 1,

1

2

` =

2

3

[ 1, 0`[

1

2

,

1

2

` +

1

3

[ 1, 1`[

1

2

, −

1

2

`

[ 7` = [

3

2

, −

3

2

, 1,

1

2

` = [ 1, −1`[

1

2

, −

1

2

`

[ 8` = [

3

2

,

3

2

, 1,

1

2

` = [ 1, 1`[

1

2

,

1

2

`

Now we can compute the matrix elements

¸

¸

¸

¸

¸

¸

¸

¸

¸

¸

¸

¸

¸

¸

¸

¸

¸

¸

¸

¸

¸

¸

¸

¸

¸

¸

¸

¸

α

0

−b 0 0 0 0 0 0 0

0 α

0

+b 0 0 0 0 0 0

0 0 α

1

−b

1/3 0 −b

√

2/3 0 0 0

0 0 0 α

1

+b(

1/3) 0 −b

√

2/3 0 0

0 0 −b(

√

2/3) 0 α

1

−b(

2/3) 0 0 0

0 0 0 −b(

√

2/3(1)) 0 α

1

+b(

2/3) 0 0

0 0 0 0 0 0 α

1

+b(−2) 0

0 0 0 0 0 0 0 α

1

+b(2)

¸

**Next we ﬁnd the eigenvalues ∆
**

i

. The energy of the state [ i` shifts by ∆

i

.

3 Variational method

3.1 Formalism

Let’s think about that helium calculation again. We approximated the wave function for

the Helium atom with two electrons as the product of the wave functions of two singly

ionized atoms. Then we included the interaction of the two electrons as a perturbation.

18

The total hamiltonian is

H =

p

2

1

2m

−

Ze

2

r

1

+

p

2

2

2m

−

Ze

2

r

2

+

e

2

[r

1

−r

2

[

with Z = 2. The approximate wave function is

[ ψ

1

`[ ψ

2

` =

Z

3

πa

3

0

1/2

Z

3

πa

3

0

1/2

e

−Zr

1

/a

0

e

−Zr

2

/a

0

Then we calculated

E

approx

= E

0

1

+E

0

2

+ ∆ = 'ψ

1

ψ

2

[ H [ ψ

1

ψ

2

` = 'ψ

1

ψ

2

[ H

0

[ ψ

1

ψ

2

` +'ψ

1

ψ

2

[ H

H

[ ψ

1

ψ

2

`

Now it is possible to write our trial wave function as a linear combination of the complete

set of exact eigenkets.

[ ψ

1

ψ

2

` =

¸

n

a

n

[ n`, H[ n` = E

n

[ n`

Then

E

approx

=

¸

n

[a

n

[

2

E

n

≥ E

0

¸

n

[a

n

[

2

So we know for sure that E

approx

≥ E

0

and in fact that will be true for any trial wave

function that we choose. It’s expectation value will always overestimate the ground state

energy. So why not try to come up with a better approximation. One adjustment that we

might make is to account for the shielding eﬀect of one electron on the other. That is, each

electron does not really see the full coulomb attraction because it is shielded by the other.

The eﬀective Z is a little less than 2. We can incorporate this approximation in our wave

function by writing

[ ψ

1

`[ ψ

2

` =

Z

3

πa

3

0

1/2

Z

3

πa

3

0

1/2

e

−Z

r

1

/a

0

e

−Z

r

2

/a

0

=

Z

πa

0

3

e

−Z

(r

1

+r

2

)/a

0

Or deﬁne a

0

= a

0

/Z

**and we get that
**

ψ

1

ψ

2

=

1

πa

3

1/2

e

−r/a

1

πa

3

1/2

e

−r/a

**Note that our new wave function is normalized. This is very important. Now we compute
**

'ψ

1

ψ

2

[ H [ ψ

1

ψ

2

` =

ψ

1

ψ

2

[

p

2

2m

[ ψ

1

ψ

2

¸

+

ψ

1

ψ

2

[

−Ze

2

r

1

+

−Ze

2

r

2

[ ψ

1

ψ

2

¸

+

ψ

1

ψ

2

[

e

2

[r

1

−r

2

[

[ ψ

1

ψ

2

¸

19

Note that ψ

1

and ψ

2

just look like the hydrogen ground state. Therefore

ψ

1

ψ

2

[

p

2

2m

[ ψ

1

ψ

2

¸

= 2

Z

e

2

2a

=

Z

2

e

2

a

0

The second term

ψ

1

ψ

2

[

−Ze

2

r

1

+

−Ze

2

r

2

[ ψ

1

ψ

2

¸

= −2Z

e

2

a

= −2

Z

Ze

2

a

0

The third term we calculated before

E

1

= e

2

Z

3

πa

3

2

e

−2Z

(r

1

+r

2

)/a

r

2

1

+r

2

2

−2r

1

r

2

cos θ

2

r

2

1

dΩ

1

r

2

2

dΩ

2

= e

2

5

8a

= Z

5

8

e

2

a

0

Therefore

'ψ

1

ψ

2

[ H [ ψ

1

ψ

2

` = (Z

2

−2Z

Z +Z

5

8

)

e

2

a

0

It will be a function of the parameter Z

**. Next, we minimize the expectation value with
**

respect to Z

. This is OK because no matter what we choose for Z

**, we know that we are
**

overestimating the energy. Set

d'H`

dZ

= (2Z

−2Z +

5

8

) = 0 →Z

= Z −

5

16

=

27

16

And

'H` = −2.85

e

2

a

0

= −77.5ev

3.2 Examples

4 Time dependent perturbation theory

4.1 Formalism

Now e want to consider time dependent perturbations. The Hamiltonian is written in the

form

H = H

0

+V (t)

We suppose that we know the complete set of eigenkets of H

0

, namely [ n` and as usual

H

0

[ n` = E

n

[ n`. We note that for a time dependent hamiltonian, the time evolution

operator is not simply e

−iHt/¯h

. Typically the time dependent part of the hamiltonian is

something that turns on and then oﬀ so it is reasonable to ask about the probability of

20

ﬁnding the system in one of the uperturbed states. An arbitrary state at t = 0 can be

written

[ α` =

¸

n

c

n

(0)[ n`

We want

[ α, t

0

= 0; t` =

¸

n

c

n

(t)e

−iEnt/¯h

[ n`

We work in the interaction picture, which is somewhere between the Schrodinger picture, in

which operators have no time dependence, but the states evolve in time, and the Heisenberg

picture in which the states are ﬁxed and the operators evolve. In the interaction picture,

we take the time dependence associated with the unperturbed Hamiltonian from states

and attach it to operators. And we attach the time dependence from the perturbation to

the states. So in the interaction picture

[ α, t

0

; t`

I

= e

iH

0

t/¯h

[ α, t

0

; t`

S

Observables are

A

I

= e

iH

0

t/¯h

A

s

e

−iH

0

t/¯h

According to the Schrodinger equation

i¯h

∂

∂t

[ α, t

0

; t`

S

= (H

0

+V )[ α, t

0

; t`

S

i¯h

∂

∂t

e

−iH

0

t/¯h

[ α, t

0

; t`

I

= (H

0

+V )e

−iH

0

t/¯h

[ α, t

0

; t`

I

i¯he

−iH

0

t/¯h

∂

∂t

[ α, t

0

; t`

I

= e

iH

0

t

V e

−iH

0

t

[ α, t

0

; t`

I

i¯h

∂

∂t

[ α, t

0

; t`

I

= V

I

[ α, t

0

; t`

I

(14)

Then we can also write that

[ α, t

0

; t` =

¸

n

c

n

(t)[ n` (15)

Substitute that last into Equation 14 and multiply from the left by 'n [ and we have

i¯h

∂

∂t

'n [ α, t

0

; t` =

¸

m

'n [ V

I

[ m` 'm [ α, t

0

; t`

I

(16)

Also from Equation 15 we see that c

n

= 'n [ α, t

0

; t`. Then

i¯h

d

dt

c

n

(t) =

¸

m

V

nm

e

iωnmt

c

m

(t)

where

ω

mn

=

E

n

−E

m

¯h

21

and we used

n [ e

iH

0

t/¯h

V (t)e

−iH

0

t/¯h

[ m

= V

nm

(t)e

i(En−Em)t/¯h

We expand the time evolution operator

[ α, t

0

; t`

I

= U

I

(t, t

0

)[ α, t

0

; t

0

`

I

i¯h

d

dt

U

I

(t, t

0

) = V

I

(t)U

I

(t, t

0

)

The initial condition is

U(t, t

0

)[

t=t

0

= 1

and we integrate to get

U

I

(t, t

0

) = 1 −

i

¯h

t

t

0

V

I

(t

)U

I

(t

, t

0

)dt

**We get an approximate solution by iteration:
**

U

I

(t, t

0

) = 1 −

i

¯h

t

t

0

V

I

(t

)

¸

1 −

i

¯h

t

t

0

V

I

(t

)U

I

(t

, t

0

)dt

¸

dt

= 1 −

i

¯h

t

t

0

V

I

(t

) +

−i

¯h

2

t

t

0

dt

t

t

0

dt

V

I

(t

)V

I

(t

)

= +. . .

4.1.1 Transition

Suppose we have a system in an eigenket [ i`. Then

[ i, t

0

; t` = U

I

(t, t

0

)[ i` =

¸

n

[ n` 'n [ U

I

(t, t

0

) [ i` =

¸

n

c

n

(t)

We see that 'n [ U

I

[ i` is the amplitude that a system initial in state [ i` will be in state

[ n` as a function of time. We note that

[ i`

I

= e

iH

0

t/¯h

[ α, t

0

; t`

S

[ i`

I

= e

iH

0

t/¯h

U(t, t

0

)[ α, t

0

; t

0

`

S

[ i`

I

= e

iH

0

t/¯h

U(t, t

0

)e

−iH

0

t

0

[ α, t

0

; t

0

`

I

→U

I

(t, t

0

) = e

iH

0

t/¯h

U

S

e

−iH

0

t

0

/¯h

Therefore

'n [ U

I

[ i` = e

i(Ent−E

i

t

0

)/¯h

'n [ U [ i`

22

Then as long as keti and [ n` are eigenkets of H

0

,

[ 'n [ U

I

[ i` [ = [ 'n [ U [ i` [

So

c

0

n

(t) = δ

ni

c

1

n

(t) = −

i

¯h

t

t

0

n [ V

I

(t

) [ i

dt

c

1

n

(t) = −

i

¯h

t

t

0

n [ V (t

) [ i

e

i(En−E

i

)t/¯h

dt

c

2

n

(t) =

−

i

¯h

2

¸

m

t

t

0

dt

t

t

0

dt

n [ V

I

(t

) [ m

m [ V

I

(t

) [ i

=

−

i

¯h

2

¸

m

t

t

0

dt

t

t

0

dt

V

nm

(t

)e

iωnmt

V

mi

(t

)e

iω

mi

t

4.1.2 Constant perturbation

We turn on a constant perturbation at t

0

. Then the amplitude to make a transition from

state i to n to ﬁrst order is

c

n

(t) = −

i

¯h

t

t

0

V

ni

e

iω

ni

t

=

−i

¯h

V

ni

iω

ni

e

iω

ni

t

−1

Then

[c

n

(t)[

2

= 4

[V

ni

[

2

¯h

2

ω

2

ni

sin

2

(ω

ni

t/2) = 4

[V

ni

[

2

(E

n

−E

i

)

2

sin

2

(ω

ni

t/2) = 4

[V

ni

[

2

(E

n

−E

i

)

2

sin

2

((E

n

−E

i

)t/2¯h)

2

If E

n

= E

i

, then [c

n

(t)[

2

=

1

¯h

2

[V

ni

[

2

t

2

If there is a ﬁnite number of ﬁnal states close to

[ n` then the total transition probability is

¸

n,En=E

i

[c

n

[

2

.

and if there are many ﬁnal states, more or less nearby we replace

¸

[c

n

[

2

→

dEρ(E

n

)[c

n

[

2

= 4

sin

2

¸

(E

n

−E

i

)t

2¯h

[V

2

ni

[E

n

−E

i

[

2

ρ(E)dE

Next we see that

lim

t→∞

sin

2

¸

(E

n

−E

i

)t

2¯h

[V

ni

[

2

[E

n

−E

i

[

2

ρ(E) =

πt

2¯h

δ(E

n

−E

i

)

23

Finally

[c

n

(t)[

2

=

ρ(E)dE[c

n

(t)[

2

=

2π

¯h

[V

ni

[

2

ρ(E

n

)t

The rate is

w

i→n

=

2π

¯h

[V

ni

[

2

ρ(E

n

)

or

w

i→n

=

2π

¯h

[V

ni

[

2

δ(E

n

−E

i

)

where integration over ﬁnal states is implied.

4.1.3 Second order perturbation

We found earlier that

c

2

n

(t) = −

1

¯h

2

¸

m

t

0

dt

t

0

dt

V

nm

(t

)e

iωnmt

V

mi

(t

)e

iω

mi

t

**If V (t) is constant in time then
**

c

2

n

(t) = −

1

¯h

2

¸

m

t

0

dt

V

nm

e

iωnmt

V

mi

e

iω

mi

t

−1

iω

mi

= −

1

¯h

2

¸

m

t

0

dt

V

nm

e

iω

ni

t

−e

iωmnt

V

mi

1

iω

mi

=

i

¯h

¸

m

V

nm

V

mi

E

m

−E

i

t

0

e

iω

ni

t

−e

iωmnt

dt

∼

i

¯h

¸

m

V

nm

V

mi

E

m

−E

i

t

0

e

iω

ni

t

dt

**Now it looks just like the ﬁrst order term with
**

−i

¯h

V

ni

→

i

¯h

¸

m

V

nm

V

ni

E

m

−E

i

So to second order

w

i→n

=

2π

¯h

V

ni

+

¸

m

V

nm

V

mi

E

i

−E

m

2

ρ(E

n

) →

2π

¯h

dE

n

V

ni

+

¸

m

V

nm

V

mi

E

i

−E

m

2

ρ(E

n

)δ(E

n

−E

i

)

The average is over all ﬁnal states n with energy E

n

∼ E

i

.

24

4.1.4 Scattering

Scattering from a ﬁxed potential is a ﬁne example of a perturbation that turns on, stays

on for awhile and then turns oﬀ. In our study of time dependent perturbation theory we

determined the the transition probability from initial state ψ

a

to ﬁnal state ψ

b

is given by

the absolute square of the amplitude

c

b

(t) = −

i

¯h

t/2

−t/2

ψ

b

[ H(t

) [ ψ

a

e

iω

ab

t

dt

where ω

ab

=

Ea−E

b

¯h

. To apply the theory to a scattering process we imagine that the

perturbation H(t

**) turns on at −t/2 and oﬀ at t/2 and while it is turned on it has constant
**

value H. Then we can integrate and we get

c

b

(t) = −

i

¯h

1

iω

ab

e

iω

ab

t/2

−e

−iω

ab

t/2

H

ab

= −

H

ab

¯h

2i sin ω

ab

t/2

ω

ab

and the transition probability is

[c

b

[

2

=

1

¯h

2

[H

ab

[

2

4 sin

2

ω

ab

t/2

ω

2

ab

=

1

¯h

2

[H

ab

[

2

sin ω

ab

t/2

ω

ab

t/2

2

t

2

Let’s examine the ω

ab

dependent piece

f(ω) ≡

sin ωt/2

ωt/2

2

t

2

The ﬁrst zero of f(ω) occurs when ω = 2π/t. Its maximum value (at ω = 0) is t

2

. In the

limit of large t, f(ω) →2πtδ(ω). To check that assertion we integrate over all ω

∞

−∞

f(ω)dω =

sin

2

x

x

2

dx

2

t

t

2

= 2πt =

2πtδ(ω)dω

In terms of the energies of initial and ﬁnal states,

2πtδ(ω) →2πt¯hδ(E

b

−E

a

)

and we can write

[c

b

[

2

=

1

¯h

2

[H

ab

[

2

2πtδ(E

b

−E

z

)

The transition rate is

R =

2π

¯h

[H

ab

[

2

δ(E

b

−E

a

)

In scattering experiments, the detector always has some ﬁnite acceptance. And what

we measure is a sum over all ﬁnal states consistent with that acceptance.

R =

2π

¯h

[H

ab

[

2

δ(E

b

−E

a

)ρ(E

b

)dE

b

25

ρ(E

b

) is the density of ﬁnal states, the number of ﬁnal states per unit energy. Well, we

have ﬁgured this out before. The number of states between k and k +dk is

dN =

V k

2

dkdΩ

8π

3

=

V p

2

dpdΩ

(2π¯h)

3

Using E = p

2

/2m and 2pdp/2m = dE we have

dN =

V pmdEdΩ

(2π¯h)

3

dN

dE

= ρ(E) =

V pm

(2π¯h)

3

dΩ

so

R =

2π

¯h

1

(2π¯h)

3

V pm[H

ab

[

2

dΩ

Now how do we connect to the cross section? The incoming particle is represented by

a plane wave

ψ

a

=

1

√

V

e

ika·r

and the outgoing wave by

ψ

b

=

1

√

V

e

ik

b

·r

The

√

V in the denominator is so that the wave function is normalized. The particle density

in the incoming wave is [ψ

a

[

2

= 1/V and the ﬂux of incoming particles is

v

V

=

p/m

V

. And

(dσ)Flux = dN = R

dσ =

R

Flux

=

V

2

m

2

(2π¯h

2

)

2

[ 'ψ

b

[ H [ ψ

a

` [

2

dΩ

dσ

dΩ

=

V m

2π¯h

2

2

[H

ab

[

2

That means that

f(θ) = −

mV

2π¯h

2

'ψ

b

[ H [ ψ

a

`

The negative sign is a convention. Suppose that H = V (r). Then

f(θ) = −

mV

2π¯h

2

1

√

V

e

−i

k

b

·r

V (r)

1

√

V

e

i

ka·r

d

3

r

= −

m

2π¯h

2

e

i(

ka−

k

b

)·r

V (r)d

3

r

The result is equivalent to that of the Green’s function analysis in the ﬁrst Born approxi-

mation. (See Griﬃths p. 368)

26

4.2 Harmonic perturbation

Now suppose that the perturbation is

V (t) = V e

iωt

+V

†

e

−iωt

We will get that

c

n

(t) = −

i

¯h

t

0

V

ni

e

i(ω

ni

+ω)t

+V

†

ni

e

i(ω

ni

−ω)t

= −

i

¯h

V

ni

e

i(ω

ni

+ω)t

−1

i(ω

ni

+ω)

+V

†

ni

e

i(ω

ni

−ω)t

−1

i(ω

ni

−ω)

If ω

ni

∼ ω then the second term is the signiﬁcant one. E

n

> E

i

and there is absorption. If

E

f

< E

i

then ω

ni

< 0 and the ﬁrst term counts. Then

[c

n

(t)[

2

=

4

¯h

2

[V

ni

[

2

sin

2

(ω

ni

±ω)t/2

(ω

ni

±ω)

2

= lim

t→∞

→

4π

¯h

2

[V

ni

[

2

δ(ω

ni

±ω)t/2

and just like for the constant perturbation

w

i→n

=

π2

¯h

2

[V

ni

[

2

πδ(ω

ni

±ω) =

2π

¯h

[V

ni

[

2

δ(E

n

−E

i

±¯hω) E

n

= E

i

±¯hω

4.2.1 Interactions with radiation ﬁeld

Let

V (t) = −

e

mc

A p

legit as long as ∇ A = 0 which is true for a plane wave in empty space. For that very

same plane wave

A = 2A

0

cos(ωt −k x) = A

0

e

i(ωt−k·x)

+e

−i(ωt−k·x)

**Consider absorption. Then we take the second term. We can expand the exponential for
**

small k. Then

A ∼ 2A

0

(1 +ik x +. . .)

In the long wavelength limit, xk → 2πx/λ is small. Small that is compared to the size of

the wave function which is perhaps the size of an atom. The typical transition energy for

an atom is

E <

Z

2

e

2

2a

0

27

The corresponding wavelength is

λ ∼

¯hc

E

=

2a

0

¯hc

Z

2

e

2

=

2a

0

Z

2

α

a

0

The transition rate in the dipole approximation is

w

i→n

=

2π

¯h

[

e

mc

A

0

'n [ p [ i` [

2

δ(E

n

−E

i

±¯hω)

The energy density of the radiation ﬁeld is U =

1

2

E

2

max

8π

+

B

2

max

8π

=

1

2π

ω

2

c

2

[A

0

[

2

. Substitution

gives us

w

i→n

=

(2π)

2

¯h

U[

e

mω

'n [ p [ i` [

2

δ(E

n

−E

i

±¯hω)

→ =

(2π)

2

¯h

ρ(ω)dω[

e

mω

'n [ p [ i` [

2

δ(E

n

−E

i

±¯hω)

=

(2π)

2

¯h

2

ρ(ω)[

e

mω

'n [ p [ i` [

2

=

(2π)

2

¯h

2

ρ(ω)[

e

mω

'n [ p [ i` [

2

=

(2π)

2

¯h

2

ρ(ω)[

e

mω

m

¯h

'n [ [H, x] [ i` [

2

=

(2πe)

2

¯h

2

ρ(ω)[ 'n [ x [ i` [

2

In the last step we use

'n [ [H, x] [ i` =

−¯h

m

'n [ p [ i` = ¯ hω

ni

'n [ x [ i`

4.2.2 Absorption vs emission

The rate that we just computed for absorption from a radiation ﬁeld with energy density

ρ(ω) is identically the rate we would ﬁnd for the emission in that same radiation ﬁeld. In

the event of spontaneous emission, we can replace ρ with an expression for the density of

ﬁnal states available to the photon.

4.2.3 Spontaneous emission

An alternative strategy for determining the spontaneous emission rate is to begin with the

expression for the stimulated rate, and then substitute the ground state radiation density

of the vacuum.

Let’s try to come up with a more systematic development.

28

The rate

w

i→n

=

2π

¯h

e

mc

A

0

2

[

n [ pe

ik·r

[ i

[

2

δ(E

n

−E

i

±¯hω)

We want to replace vector potential with energy density. We use

U =

1

2π

ω

2

c

2

[A

0

[

2

Then

w

i→n

=

2π

¯h

2πc

2

ω

2

U

e

mc

2

[

n [ pe

ik·r

[ i

[

2

δ(E

n

−E

i

±¯hω)

U has some frequency dependence. The total energy density is

ρ(ω)dω = U

We replace U with ρ(ω)dω and integrate with the δ function. We get

w

i→n

=

2π

¯h

2

2πc

2

ω

2

ρ(ω

ni

)

e

mc

2

[

n [ pe

ik·r

[ i

[

2

What do we mean by ρ(ω)? It is the energy density per unity volume per unit frequency.

The density at the frequency corresponding to the transition energy is the only part that

counts. The transition rate from n → i or in the other direction is exactly the same, in

one case it is absorption and in the other it is stimulated emission. How do we get from

here to spontaneous emission?

It must be that there is some vacuum ﬂuctuation or vacuum radiation density. We

need second quantization for a mathematically complete theory. But we can develop an

expression for spontaneous emission based on a heuristic argument. We simply replace the

expression for the radiation density with the energy density of available photon states. The

total number of states with energy E < ¯hkc, where k

x

= πn

x

/L, etc. is

N =

1

8

4

3

π(n

2

x

+n

2

y

+n

2

z

)

3/2

=

1

8

4

3

π

L

π

3

(k

2

)

3/2

=

π

6

L

π

3

(

ω

c

)

3

1

V

dN

dω

=

1

2π

2

ω

2

c

3

number of states per unit volume per unit frequency

29

Finally to get the energy density we multiply by two to include the two polarization states

and multiply by ¯hω, the energy of the photon in the state and we end up with

ρ(ω) =

¯h

π

2

ω

3

c

3

The spontaneous transition rate becomes

w

i→n

=

4π

¯h

2

2πc

2

ω

2

¯h

2π

2

ω

3

c

3

e

mc

2

[

n [ pe

ik·r

[ i

[

2

= 4

ω

¯hc

e

mc

2

[

n [ pe

ik·r

[ i

[

2

= 4 (ω)

α

mc

2

1

m

[

n [ pe

ik·r

[ i

[

2

which sure enough is a rate. In the dipole approximation we get

w

i→n

= 4 (ω)

α

mc

2

1

m

[mω 'n [ x [ i` [

2

= 4

ω

3

α

c

2

[ 'n [ x [ i` [

2

4.2.4 Average over polarization and angle

To get the total spontaneous emission rate we average that last over all directions k for

the outgoing photon and all polarizations . Suppose that x is along the z-direction and

the outgoing photon is at an angle θ, φ = 0. First note that if θ = 0, then x = 0.

So project onto the x-axis. Then the polarization is in the y-z plane and the average of

' ˆz`

2

=

1

4π

sin

2

sin θdθ

cos

2

αdα =

1

4π

(

4

3

)π =

1

3

. The total spontaneous decay rate into

all angles and polarizations is

w

i→n

=

4

3

ω

3

α

c

2

[ 'n [ x [ i` [

2

4.2.5 Angular distribution

Suppose we know that the transition is E1 and ∆m = 1. Since it is E1 that means that

∆l = ±1 by Wigner Eckart. Then

'f [ x [ i` = 'l ±1, m±1 [ x [ lm`

30

will be a vector in the x-y plane. No z-component. That means that if the photon is headed

in the z-direction x = 1 for all polarizations. If it is headed in the x-direction then we

need to average. The angle θ is that of the polarization with respect to the y-axis.

1

2π

cos

2

θdθ =

1

2

For a photon headed in the θ direction with respect to the z-axis, it has a component cos θ

in the z-direction and and component sin θ in the x-direction. We get all of the z-direction

piece and half of the x-direction piece so the probability to go into the angle θ is

P(θ) = cos

2

θ +

1

2

sin

2

θ =

1

2

(1 + cos

2

θ)

which happens to be the same

[d

1

1,1

[

2

+[d

1

1,−1

[

2

=

1

2

(1 + cos θ)

2

+

1

2

(1 −cos θ)

2

=

1

2

(1 + cos

2

θ)

4.2.6 Absorption cross section

Or instead of writing the rate in terms of the energy density of the incident radiation, we

could deﬁne the cross section. Then the rate is the incoming ﬂux times the cross section.

The incoming energy ﬂux is the energy density times the velocity. The ﬂux of photons is

the energy ﬂux/photon energy. So

Rate = σFlux and Flux = cU/¯hω

Then

σ

abs

=

w

i→n

¯hω

cU

=

(2π)

2

c

e

2

m

2

ω

[ 'n [ p [ i` [

2

δ(E

n

−E

i

±¯hω)

Again we replace 'p` with m/¯h'[H, x]` and get that

σ

abs

=

(2π)

2

c

ωe

2

¯h

2

[ 'n [ x [ i` [

2

δ(E

n

−E

i

±¯hω) =

(2π)

2

c

ωe

2

¯h

[ 'n [ x [ i` [

2

δ(ω

ni

−ω)

If we suppose the polarization is in the x direction then The total absorption cross section

is

σ(ω)dω =

¸

n

4π

2

ω

ni

α[ 'n [ x [ i` [

2

4.3 Photo electric eﬀect

Imagine a hydrogen atom at rest at the origin. Electromagnetic radiation in the form of

a plane wave is propagating in the +z direction (k = [k[ˆ z) with E-ﬁeld polarized along

the x-direction. The radiation ﬁeld interacts with the atom and frees the electron. The

electron ﬂys oﬀ in the (θ, φ) direction with momentum p = ¯ hk

f

31

4.3.1 Golden rule

The transition rate is given by the golden rule

R =

[ 'f [ H

[ i` [

2

¯h

2πδ(E

f

−E

i

−¯hω)

The initial state is the ground state of hydrogen

'x [ i` =

2

√

4πa

3

e

−r/a

The ﬁnal state is a free electron

'x [ f` =

1

L

3/2

e

ik

f

·r

which we represent as a plane wave. We imagine the plane wave in a box with sides of

length L so that it is normalized over the volume. We assume that the energy of the

electron is so high that we can neglect the eﬀect of the coulomb attraction of the hydrogen

nucleus in the ﬁnal state.

4.3.2 Interaction Hamiltonian

The interaction hamiltonian is

H

=

q

mc

A p

We write the vector potential as a plane wave,

A = 2A

0

cos(k r −ωt) (17)

= A

0

e

i(k·r−ωt)

+e

−i(k·r−ωt)

(18)

where is the unit vector that gives the polarization of A and E = −

∂A

∂t

After application

of the energy conserving δ-function we are left with

A = A

0

e

i(k·r−ωt)

Then

H

=

−i¯hq

mc

A

0

e

ik·r

∇

32

4.3.3 Density of states

The free electron in the ﬁnal state is traveling at angle θ, φ into solid angle dΩ. In order to

determine the total rate for the transition we need to integrate over all possible ﬁnal state

electrons that are directed into the solid angle. The electrons are free particles conﬁned to

a box with side L. The electron wave function at the boundaries vanishes so

k

x

=

2n

x

π

L

, k

y

=

2n

y

π

L

, k

z

=

2n

z

π

L

and

k

2

f

=

2π

L

2

(n

2

x

+n

2

y

+n

2

z

)

Imagine a sphere of radius

n

2

x

+n

2

y

+n

2

z

. The total number of states with [k[ < [k

f

[ is

the volume of the sphere,

N =

4

3

π(n

2

x

+n

2

y

+n

2

z

)

3/2

=

4

3

π

L

2π

k

2

3/2

The number of states per unit k into solid angle dΩ are

dN

dk

=

4

3

π

L

2π

3

3k

2

dΩ

4π

The number of states per unit energy into solid angle dΩ are

dN

dE

=

L

2π

3

k

2

dk

dE

dΩ

4π

(19)

=

L

2π

3

km

¯h

2

dΩ (20)

where we have use E =

¯h

2

k

2

2m

.

4.3.4 Transition rate

The total transition rate is

R =

[ 'f [ H

[ i` [

2

¯h

2π

δ(E

f

−E

i

−¯hω)

dN

dE

(21)

=

[ 'f [ H

[ i` [

2

¯h

2π

L

2π

3

km

¯h

2

dΩ (22)

= ¯h

qA

0

mc

2

[

f [ e

ik·r

∇ [ i

[

2

2π

L

2π

3

km

¯h

2

dΩ (23)

33

4.3.5 Absorption cross section

We deﬁne a diﬀerential cross section

dσ

dΩ

=

Rate for photoelectrons

Flux of incident photons

The energy ﬂux for the incoming plane wave is

cu =

c

8π

E

2

max

=

1

2π

ω

2

c

A

2

0

and since each photon has energy ¯hω, the photon ﬂux is

Flux =

1

2π¯hωc

ω

2

A

2

0

=

1

2π¯hc

ωA

2

0

Then

dσ

dΩ

=

¯h

q

2

A

2

0

(mc)

2

[

f [ e

ik·r

∇ [ i

[

2

2π

L

2π

3

km

¯h

2

(ωA

2

0

/2π¯hc)

(24)

=

2π(q¯h)

2

[

f [ e

ik·r

∇ [ i

[

2

2π

L

2π

3

km

¯h

2

m

2

cω

(25)

=

q

2

[

f [ e

ik·r

∇ [ i

[

2

L

3

k

2πmcω

(26)

4.3.6 Expectation value

All that remains is to compute the expectation value. Note that it is not appropriate to

work in the electric dipole limit. We are assuming that the energy of the ﬁnal state electron

is big compared to the binding energy. Therefore it is not safe to assume that k r < 1

and we will attempt to do the integral exactly.

We have that

f [ e

ik·r

∇ [ i

=

1

L

3/2

1

π

1/2

a

3/2

I

where

I =

e

−ik

f

·r

e

ik·r

∇e

−r/a

r

2

drdΩ

Integrating by parts we get that

I =

∇

e

−ik

f

·r

e

ik·r

e

−r/a

r

2

drdΩ (27)

−

∇

e

−ik

f

·r

e

ik·r

e

−r/a

r

2

drdΩ (28)

−

e

−ik

f

·r

∇

e

ik·r

e

−r/a

r

2

drdΩ (29)

34

Equation 11 can be written as a surface integral over a volume that we can take to inﬁnity.

The wave function falls oﬀ exponentially so Equation 27 is zero. On taking the gradient

Equation 29 and pulling k outside of the integral, we get

i k

e

−ik

f

·r

e

ik·r

e

−r/a

r

2

drdΩ = 0

since polarization and propagation vector k are orthogonal. Finally

I =

∇

e

ik

f

·r

e

ik·r

e

−r/a

r

2

drdΩ (30)

= −i k

f

e

−ik

f

·r

e

ik·r

e

−r/a

r

2

drdΩ (31)

= −i k

f

e

−i(k

f

−k)·r

e

−r/a

r

2

drdΩ (32)

= −i k

f

e

−iq·r

e

−r/a

r

2

drdΩ (33)

= −i k

f

e

−iq cos θr

e

−r/a

r

2

dr sin θdφ (34)

where q = k

f

−k. First we do the angular integral

I = i2π k

f

(e

−iqr

−e

iqr

)

iqr

e

−r/a

r

2

dr (35)

Then integrate over r.

I = 2π k

f

(e

−iqr−r/a

−e

iqr−r/a

)

iq

rdr (36)

= 2π k

f

1

q(−iq −1/a)

2

−

1

q(iq −1/a)

2

(37)

= 2π k

f

1

q(−q

2

+ 1/a

2

−2iq/a)

−

1

q(−q

2

+ 1/a

2

+ 2iq/a)

(38)

= 2π k

f

−4iq/a

q((−q

2

+ 1/a

2

)

2

+ 4(q/a)

2

)

2

(39)

= 2π k

f

−4i

a(q

2

+ (1/a)

2

)

(40)

Finally

f [ e

ik·r

∇ [ i

=

1

L

3/2

1

π

1/2

a

3/2

2π k

f

−4i

a(q

2

+ (1/a)

2

)

2

(41)

=

−8iπ

1/2

k

f

L

3/2

a

3/2

a(q

2

+ (1/a)

2

)

2

(42)

(43)

35

and

dσ

dΩ

=

α¯hL

3

k

f

2πmω

8π

1/2

k

f

L

3/2

a

5/2

(q

2

+ (1/a)

2

)

2

2

(44)

=

32α¯hk

f

mω

( k

f

)

2

a

5

(q

2

+ (1/a)

2

)

4

(45)

4.3.7 Angular distribution

The E-ﬁeld vector k is in the z-direction and the electron in the ﬁnal state has k

f

in the

θ, φ direction. Then q

2

= k

2

f

+ k

2

− 2k

f

k cos θ. And the polarization is in the x-direction

so that k

f

= k

f

sin θ cos φ and

dσ

dΩ

==

32α¯hk

f

mω

(k

f

sin θ cos φ)

2

a

5

(k

2

f

+k

2

−2k

f

k cos θ + (1/a)

2

)

4

The diﬀerential cross section is peaked for the outgoing electron in the θ = π/2, φ = 0

direction, namely parallel to the polarization of the ﬁeld.

36

To make sure we don’t do something crazy like divide by zero we project out the | n0 ket by introducing a projection operator φ=

k=n

| k0 k0 |

**Then we make the equation safe from nan. |n =
**

0 En

φ (λV − ∆n )| n − H0

We are not losing anything here since Equation 3 says that n0 | λV − ∆n | n = 0 (4)

**Finally, so we have something sensible as λ → 0 we add the solution to the unperturbed part and write | n = | n0 +
**

0 En

φ (λV − ∆n )| n − H0

One last thing to note. Normalization. It seems that n | n0 = 1. We will use this fact. | n is not normalized by itself. Now Equation 4 says that ∆n = λ n0 | V | n Now we suppose that | n = | n0 + λ| n1 + λ2 | n2 + . . . and ∆n = λ∆1 + λ2 ∆2 + . . . n n Then equation powers of λ. Our energy equation becomes λ∆1 + λ2 ∆2 + . . . = λ n0 |V | n0 + λ| n1 + λ2 | n2 + . . . n n So ∆1 = n ∆2 = n ∆3 = n n0 | V | n0 n0 | V | n1 n0 | V | n2

2

**And for the wave function | n0 +λ| n1 +λ2 | n2 +. . . = | n0 + Equating stuﬀ linear in λ we get | n1 = Next everything quadratic in λ gives | n2 = | n2 =
**

0 En 0 En 0 En

φ (λV −(λ∆1 −λ2 ∆2 +. . .))| n0 +λ| n1 +λ2 | n2 +. . . n n − H0

φ V | n0 − H0

(5)

φ V | n1 − ∆1 | n1 n − H0

0 En

φ φ φ V 0 V | n0 − n0 | V | n0 0 V | n0 − H0 En − H0 En − H0

And we can use our solution for | n1 to see that ∆2 = n0 |V n | n0 | V | k0 |2 φ V | n0 = 0 0 0 En − H0 En − Ek k=n

It is evident that degeneracy could get us in trouble.

1.2

1.2.1

Examples

Helium

To ﬁrst approximation, the energy of the ground state of helium is 2Z 2 E0 = −2Z 2 e2 2a = 2(4)(−13.6ev) = −108.8ev

The next approximation would be to include the interaction of the electrons as a perturbation. e2 V = |r1 − r2 | The unperturbed wave function is taken to be ψ(r1 , r2 ) = ψ0 (r1 )ψ0 (r2 ) = 3 8 −2(r1 +r2 )/a e πa3

2 −e2 2a + 5e2 11e2 11 =− = − (13.m Y1. (Wigner Eckart).2. m2 | T0 | l1 .m dΩ 4 . m | T0 | l.where a= Set the polar axis along r1 and E 1 = e2 8 πa3 2 hc ¯ αmc2 e−4(r1 +r2 )/a 2 2 r1 + r2 − 2r1 r2 cos θ2 2 2 r1 dΩ1 r2 dΩ2 = e2 5 4a Then the total energy is E = 2(4) 1. l1 = l2 .8ev 4a 4a 2 Stark eﬀect for rigid rotator The hamilonian for the rigid rotator is H= L2 2I where I is the moment of inertia and the vibrational levels are assumed inﬁnitely far apart as compared to the spacing of the rotational levels.0 (θ) 3 We need to evaluate 1 l2 .0 Yl. m = −dE 4π 3 ∗ Yl±1. (parity).6ev) = −74. m1 The matrix element is non zero if m1 = m2 and (|l2 − l1 | ≤ 1. Then the energy eigenstates h2 and eigenvalues are | ψ = | l. m and El = ¯ l(l+1) . (All states have the same radial wave function). We can write 1 V = T0 = −dE 4π Y1. In the presence of a uniform 2I electric ﬁeld in the z direction we introduce V = −ezE = −erE cos θ We suppose that e r = d is the electric dipole moment of the rotator. Then the non zero matrix element can be written 1 l ± 1.

l. The second order correction reduces to the two terms corresponding to l = ±1. since it depends on m2 . l. Some symmetry remains. 0. l. it does commute with Lz . But since H0 and V both commute with Lz . ( l. 0 | l ± 1. m | l ± 1. and non degenerate theory is OK. Finally lm 2 = dE El0 2 l(l + 1) − 3m2 2(2l − 1)(2l + 3) The degeneracy is only partly removed. Also. Another way to see this is to note that although the perturbed Hamiltonian does not commute with L2 . We could compute the electric dipole moment. the perturbation commutes with Lz so there is no mixing of states with diﬀerent m and we use non degenerate perturbation theory.3 Stark eﬀect in hydrogen As in the case of the rigid rotator. m 1. 0. So there is no change to the z-component and therefore no mixing of states with 5 . m 1. 0. 0. by the 1 rules above. there is no mixing. m | T0 | l. m | l ± 1. since all of the eigenstates with deﬁnite angular momentum have deﬁnite parity. 0 (2(l ± 1) + 1) l2 − m2 4l2 − 1 The unperturbed levels are all degenerate.2. The ﬁrst order correction is zero. µ∼e n|z|n We have that | n ∼ | n0 + k=n 1 k0 | T0 | n0 | k0 0 0 En − Ek Then µ∼ k=n 1 n0 | z | k0 k0 | T0 | n0 1 = 0 − E 0) (En E k 1 1 n0 | T0 | k0 k0 | T0 | n0 0 0 (En − Ek ) k=n 1. 0 | l ± 1. the spectrum is non degenerate. there is no ﬁrst order correction.= −dE = −dE = −dE 4π 3 (2(1) + 1)(2l + 1) 1. 0 4π(2(l ± 1) + 1) (2l + 1) 1. m = 0. l. In each of the m supspaces.

The strategy is to ﬁnd a new basis for the degenerate states in which none of the states in that basis are coupled by the perturbation.m = m . (this will give us an upper limit on the energy shift) and noting that | k 0 | z | 1. 0. it is OK as long as the perturbation does not couple the degenerate states. m | x | α. The sum over all k becomes | k 0 | z | 1. 0. 0. 0. l. If it does couple degenerate states we are in trouble since then we have ﬁnite numerator and an energy denominator that is zero in Equation 5. 0 = all k 1 2 r = a2 0 3 Therefore. But actually. 0. 0 | z | 1. 0. 0. 0 | z 2 | 1. 0 = 1. m = x|ψ(x)|2 d3 x = 0 since x has odd parity. 0 |2 = k=0 all k | k 0 | z | 1. The energy shift is quadratic in E The polarizability is α where 1 ∆ = − α|E|2 2 The energy shift is second order ∆2 = e2 E 2 | k 0 | z | 1. The electric dipole moment is d = α. ∆2 ≤ e2 E 2 a2 a2 8a3 0 0 = ∆2 ≤ e2 E 2 = −E 2 0 0 0 (E0 − Ek ) 3 (−e2 /2a0 − −1 e2 /2a0 ) 4 2 Degenerate perturbation theory Our formalism falls apart if there are degeneracies. 0 since 1. 0. An electric dipole emerges in second order since the ﬁrst order correction to the wave function includes contributions of opposite parity. l. 0 = 0. 6 . Parity eigenstates have zero electric dipole moment. 0 |2 0 0 (E0 − Ek ) k=0 We approximate the sum by assuming that the denominator is constant. That also means that the electric dipole moment scales with the applied electric ﬁeld.

The ﬁrst order shift in the state vector is given as before by | n1 = k=D k 0 | V | n0 | k0 0 0 (En − Ek ) The states in the degenerate subspace do not contribute because all of the oﬀ diagonal matrix elements are zero. then we need to ﬁnd a diﬀerent linear combination of the degenerate states for which the perturbation matrix is diagonal. We go back to the Schrodinger equation 0 = (E − H0 − λV )| l = (E − ED − λV )P0 | l + (E − H0 − λV )P1 | l Projecting from the left by P0 and P1 we get P0 ((E − ED − λV )P0 | l + (E − H0 − λV )P1 | l ) = (E − ED − λP0 V P0 | l − λP0 V P1 | l P1 ((E − ED − λV )P0 | l + (E − H0 − λV )P1 | l ) = −λP1 V P0 | l + (E − H0 − λP1 V P1 )| l 7 (6) (7) .1 Formalism So here’s what we do. i = 1. Likewise for the second order correction to the energy. In fact we see that the eigenvalues are the ﬁrst order energy shift.1 Projection operators We could more formally use the projection operator approach. Now if i | V | j = |V |δij then we do not have a problem. That is we diagonalize 1|V |1 V = 2|V |1 3|V |1 1|V |2 2|V |2 3|V |2 1|V |3 I|V |I 2|V |3 → 0 3|V |3 0 0 II | V | II 0 0 0 III | V | III The new basis is related to the old by a unitary transformation. Business as usual. If there are oﬀ-diagonal terms. 2.1. | III are the eigenkets of the perturbation matrix and the diagonal elements of the perturbation matrix in the new basis are the eigenvalues. | II .2. 3 for example. 2. Suppose that there is a degenerate set of states and we are interested in the eﬀect on the perturbation of states at that energy. | I = a| 1 + b| 2 + c| 3 The states | I . The states are | i .

Here | l0 = i=D (9) ai | i | l0 is a normalized linear combination of the degenerate states in the basis in which the perturbation matrix is diagonalized. . |l = ai | li 1 λP1 V )P0 | l E − H0 − λP1 V P1 Then the Schrodinger equation including the perturbation is (El0 − H0 )| l = (λV − ∆n )| l Substitute the expansion for ∆l and | l = | l0 + λ| l1 + λ2 | l2 + . Multiply by m0 | from the left 0 m0 | En − H0 | l = λ m0 | V | l − ∆l m0 | l and keep the ﬁrst order in λ. The exact state vector is a linear combination of all | l0 kets. . . and the all the rest. In summary we divide the space into the subspace of degenerate states.We solve Equation 7 for | l and then project out the states not part of the degenerate subspace and then the denominator is safe P1 | l 1 λP1 V P0 | l E − H0 − λP1 V P1 k 0 | V | l0 ∼ P1 | l 1 ∼ | k0 0 0 ED − Ek k=D = P1 (8) Then substitute Equation 8 into Equation 6 for P1 | l multiply by P0 and we have (E − ED − λP0 V P0 − λP0 V P1 ∼ (E − ED − λP0 V P0 )| l = 0 The energies are the eigenvalues of the perturbation matrix. when m0 = lD and we get that 0 = lD | V | l0 − ∆1 lD | l → lD | V lD = ∆i l D When m0 = lD 0 0 (En − Em ) m0 | l = λ m0 | V | l − ∆l m0 | l 8 .

. We deﬁne | l1 and all higher order contributions to include no | l0 or for that matter any of the | lD degenerate states. The above gives no information about them. . for j = 0. We suppose that the ai are chosen so that | l0 is normalized.1. and | l0 = i=D ai | i l0 | lj = 0. We know that (H − Ea )| a = (H0 + λH1 − Ea )| a = 0 1 Gottfried and Yan 9 .2 Second order degenerate perturbation theory Another strategy1 for getting second order correction of degenerate states is to write the true state |a = cα | α + dµ | µ α µ where the sum over α includes the degenerate states and the sum over µ is all the others. We see that in this way | l is a solution to Equation 9 independent of the coeﬃcients ai . And the second order energy shift ∆2 = l0 | V | n1 = l 2. Then the exact solution is |l = i=D ai | i + | l 1 + | l 2 + .To ﬁrst order in λ we have 0 0 (En − Em ) m0 | l1 = m0 | V | l0 and m0 | l1 ∼ and | l1 = l=D m0 | V | l0 0 El0 − Em m0 | V | l0 | m0 0 0 En − Em Note that we can always add states with eigenvalue El0 .

That would be equivalent to solving for dν = −λ Substitution into 10 gives 0 = cβ (Eβ − Eα ) + α α cα ν | H1 | α (Eν − ED ) (12) cα λ β | H1 | α + λ2 µ µ | H1 | α β | H1 | µ Eµ − ED (13) which is the eigenvalue problem in the subspace D for the eﬀective Hamiltonian Hef f β | Hef f | α = λ β | H1 | α + λ2 µ β | H1 | µ µ | H1 | α . P = α | α α |. You might then argue that we should drop the last term in Equation 10. Then that last term is second order in λ.Then 0 = α cα (H − Ea )| α + µ dµ (H − Ea )| µ dµ (Eµ − Ea + λH1 )| µ µ 0 = α cα (Eα − Ea + λH1 )| α + Then multiply from the left ﬁrst by β | which is an element of the degenerate space and then by ν | which is outside of the degenerate space. Then we can write Hef f = λP H1 P + λ2 P H1 10 1−P H1 P E − H0 . 0 = cβ (Eβ − Ea ) + λ α cα β | H1 | α + λ µ dµ β | H1 | µ dµ ν | H1 | µ µ (10) (11) 0 = α cα λ ν | H1 | α + dν (Eν − Eα ) + λ Drop the last term in Equation 11 as it is higher order in λ. we could keep the last term in Equation 11. The coeﬃcients dµ would all be zero in the λ → 0 limit so they are at most ﬁrst order in λ. Justiﬁcation for this step is that the state | a is mostly a linear combination of the states in the degenerate space. Deﬁne P to be the projection operator onto the degenerate subspace D. substitute into Equation 10 and then drop the highest order term. but probably β | H1 | µ is more important that ν | H1 | µ since it connects to the relevant states. Finally. solve for dν . ED − Eµ So we diagonalize β | H1 | α .

The ﬁrst two are degenerate.2. if ∆ ∼ λM . The eigenvectors 2 are E± (| 1 + | 2 + λM | 3 ) 1 | 0 = √ (| 1 − | 2 ). ∆ 1 | ES = √ (| 1 + | 2 ) 2 0 0 λM λM λM ∆ 1 1 1 1 (λM )2 ∆ 1 | ES = √ (| 1 − | 2 ) 2 That’s what happens if ∆ λM . 0 H1 = 0 λM The Hef f = − The energies and eigenstates are ES = −2 and (λM )2 .3 Example Suppose we have a system with 3 states. Assume the unperturbed energies are all the same. What if we went back to the weak perturbation case where M ∆. The third is at energy ∆ above the two. E± = 1 (∆ ± ∆2 + 8(λM )2 ). E0 = 0. Then the shift in the energy of each of the three states is given by the eigenvalues of H1 which are. Then √ 0 0 2M V = √0 0 0 2M 0 ∆ Now Hef f = −2M 2 /∆ 0 0 0 11 . then we treat all three states as though they were degenerate.1. On the other hand. but we had 1 1 started with states | S = √2 (| 1 + | 2 ) and | A = √2 (| 1 − | 2 ) and | III = | 3 . | ± = 2 2 2 + E± /λ2 M 2 EA = 0.

or we can take the linear 12 .2. The best way to do this is to take the nonrelativistic limit of the Dirac equation with a vector potential.1 Fine Structure Spin orbit coupling The magnetic ﬁeld at the electron due to its motion through the E ﬁeld of the nucleus is v×E B=− c The electric ﬁeld is radial so E = B= Next. s. note that E = 1 e |E| r r and p = mv and then r × p |E| L |E| = mc r mc r and we get that B= L 1 ∂V mec r ∂r V = 1 ∂V e ∂r The magnetic moment of the electron is µe = − Finally ∆H = −µ · B = and if V = e/r then e2 L · S e2 L · S → m2 c2 r3 2m2 c2 r3 1 Then a factor of 2 for the Thomas Precession. ml | s.2. We can use | l. Or we could use the Biot Savart Law which states that ∆H = B= (JdV )×r c|r|3 1 m2 c2 r ∂V L·S ∂r e S mc For a current loop. m. ms as base kets with eigenvalues l.2 2. we ﬁnd the magnetic ﬁeld at the center is B= I cr3 eλdlv × r = − er × p cmr3 The unperturbed states have orbital angular momentum and spin. and ms .

Each level is split into j = l ± 1 .combinations that would be eigenkets of j. s. it 2 is clear that it will be more convenient to use the latter. 2 2. jz . No mixing of levels.2 Really K= (mc2 )2 + (pc)2 − mc2 ∼ 13 p2 p4 − 2m 8m3 c2 Relativistic correction . No need for degenerate formalism. Since L · S = 1 (J 2 − L2 − S 2 ). l.2. Then 1 En ESO e2 h2 1 ¯ 3 = j(j + 1) − l(l + 1) − 2 c2 r 3 4m 4 [j(j + 1) − l(l + 1) − 3/4] h2 e2 1 ¯ = 1 4m2 c2 n3 a3 l(l + 2 )(l + 1) 0 1 1 = 3 3 r3 n a0 l(l + 1/2)(l + 1) where For j = l ± 1 2 ESO l h2 e2 1 ¯ −(l + 1) = 1 4m2 c2 a3 n3 l(l + 2 )(l + 1) 0 mc2 α4 = 4 l −(l + 1) n3 l(l + 1 )(l + 1) 2 We remember that 1 e2 e2 h2 ¯ E0 = − α2 mc2 = − → a0 = 2 2 = 2 2a0 α mc me2 Substitution into the above gives 1 En ∼ h2 c2 (α2 mc2 )3 ¯ 1 3 e2 h2 (α2 mc2 )3 ¯ = = α2 mc2 (α2 ) j(j + 1) − l(l + 1) − 2 c2 e6 4 (mc2 )2 2m 2e 2 4 No dependence on ml .

Again there is no mixing of degenerate levels. The ¯ potential that is relevant is not V (r) but some smeared average about the point r. 0.3 Darwin term 1 1 = 1 2 r (l + 2 )n3 a2 0 The particle cannot be localized to better than its Compton wavelength h/mc. 0. r n a0 2.And ψ| p4 2m |ψ = = p2 p2 ψ| ψ = (E0 − V )ψ | (E0 − V )ψ 2m 2m 2 ψ | (E0 − 2E0 V + V 2 | ψ We use the fact that p2 is Hermitian in the ﬁrst step.2. 1 ∆E0 ∼ − (2m)2 (En − V (r))2 8m3 c2 ∼ −e2 e4 4m2 2 En − 2En + 2 8m3 c2 r r −e2 e4 4m2 2 ∼ − 3 2 En − 2En 2 + 1 8m c n a0 (l + 2 )n3 a3 0 ∼ − ∼ − ∼ − 4m2 2 4n E 1−4+ 3 c2 n 8m (l + 1 ) 2 1 4n E 2 −3 + 2 n 2mc (l + 1 ) 2 1 mc2 α4 4n −3 + 1 2 4n4 (l + 2 ) 5 1 5 ∼ − E0 ( α2 mc2 ) = E0 α2 2mc2 2 4 (Note that 1. 0 = a22 . 0 | r12 | 1. V (r) = V (r) + i ∂V 1 δri + ∂ri 2! 2 i j ∂ 2V δri δrj + O(δr3 ) ∂ri ∂rj 1 = V (r) + (δr)2 6 V + O(δr3 ) 14 . 0 = a10 and 1.) Depends on n. In general 1 1 = 2 . r 0 not on j. 0. 0. l. 0 | 1 | 1.

4 Fine Structure 1 n! = 3 2n(n − 1)! (na) 1 2(na0 )3 Combining all order α2 corrections we have ESO = 2 En mc2 n[j(j + 1) − l(l + 1) − 3/4] l(l + 1 )(l + 1) 2 The relativistic correction is 1 Er 2 4n En −3 =− 2 l+ 1 2mc 2 The total α2 correction is − E1 α2 1+ 2 n2 n n j+ 1 2 − 3 4 2.m (0) = Then 2π 1 2 e2 h2 ¯ ¯ 1 2π e2 h2 1 m3 e6 = n00 | HD | n00 = π 2 2 = mc2 α4 3 2 c2 2n3 h6 3 m c 2(na0 ) 3 m 3 2n3 ¯ and it exactly compensates for the l = 0 term that we got from the spin orbit term.3 Stark eﬀect To determine the eﬀect of an external uniform electric ﬁeld on a set of degenerate levels we need to exercise a bit more care. There are 2l+1 = 3 levels with l = 1 and 1 level with l = 0. Consider n = 2 in hydrogen. Spin is not relevant. 206 and 208) ψn. The candidate 15 .2. 2.If δr ∼ h/mc then ¯ 2 e2 h2 ¯ HD ∼ π 2 2 δ 3 (r) 3 mc Note that according to Merzbacher (p.l. Or it would if we did it properly using the Dirac equation.

m. 0 ) 2 These two states are shifted positively and negatively with an electric ﬁeld. 0. The perturbation matrix elements i | V | j . 0. 0. 1. 0 | cos θ | 2. s | Lz + 2Sz | j. 0 0 0 2. All of the other states are not coupled. we need to evaluate j. 1.m = ± | l. l. 1. l. The eigenvectors of the upper left 2X2 matrix are ∆1 = − ± e|E| 2. m | Sz | l ± . 0 0 0 0 0 0 0 0 0 0 0 0 Only the upper left is relevant. 0 | V | 2. l. The other 2 states are not eﬀected by the E-ﬁeld. m. 1 2. m = ± 2 2 2l + 1 16 l m+ 1 1 1 1 2 | l. 1.4 Zeeman eﬀect H= e e2 p2 + Vc (r) − |B|Lz + |B|2 (x2 + y 2 ) 2m 2mc 8mc2 HZ = − e |B|(Lz + 2Sz ) 2mc e e S · B = − |B|Sz mc mc We have and then Hspin = −µ · B = − and 1 1 dV (r) L·S 2m2 c2 r dr Assuming B is very weak so that the spin-orbit piece dominates. m. m. 0 = ±3ea0 |E| ± The eigenvectors are 1 | ± = √ (| 2. l. + 2 2l + 1 2 2 2 we can compute 1 1 m¯ h l ± . 2.set of base states are the orbital angular momentum kets. s Since Hspin−orbit = l±m+ 1 1 1 1 1 2 | l ± . 0 | r | 2. s | Jz + Sz | j. 0 ± | 2. 0 | V | 2. m + | . s = j. m − | . 0. where V = −ez|E| are V = 0 2. − 2l + 1 2 2 2 .

l. ±1/2. m = hm. j = ±3/2. = 2 2 2 1 1 1 | 1.1 Paschen-Back limit e¯ B h 1 m 1± 2mc 2l + 1 If the magnetic ﬁeld is very strong. −1 | .1 Meanwhile l ± 1 . . 0. 0. − 2 2 2 2 2 1 1 1 1 1 = | . 0. So let’s look at the eﬀect of the external ﬁeld. ms = ±1/2. (l = 1. We had better label the states. 1. − . And we suppose that Hspin−orbit ≈ Hz . It is easy to evaluate Lz + 2Sz but not quite as simple to compute L · S for the spin orbit coupling. Then ¯ 2 ∆1 = − B 2. s. Then the L · S term only contributes along the diagonal. (There is an external torque). We have to construct the perturbation matrix elements i | V | j in whatever basis we have chosen and V =− e2 1 e B(Lz + 2Sz ) + L·S 2mc 2m2 c2 r3 Let’s pick the basis of eigenstates of j. m | Jz | l ± 2 . 0 | . 3 2 2 . − − 3 2 2 17 2 1 1 | 1. j = ± 2 or eigenstates of l. l = 0. l. then total angular momentum is not conserved. Now we have to exercise some care in computing energy shifts.or l = 0. There are 8 degenerate states. We can choose as a basis 1 eigenstates of j. = | 0. 0 | . |1 |2 |3 1 1 1 1 1 = | . (l = 1. ml | s.4. But the Lz and Sz are ﬁxed.2 Intermediate ﬁeld Let’s examine the eﬀect of an external magnetic ﬁeld on the n = 2 states of hydrogen. s. − . But if we write 1 L · S = Lz Sz + (L+ S− + L− S+ ) 2 and note that L± = S± = 0 then we get that L · S = h2 ml m2 ¯ 2. jz . 2 2 2 2 2 1 1 1 = | .4. s. jz . ms . = | 0. ms . 0 | . ml . ms = ±1/2). So now it is better to use the basis | . ml = ±1.

− 3 2 2 Now we can compute the matrix elements α0 − b 0 0 0 0 0 0 0 0 α0 + b 0 0 0 0 0 0 0 0 α1 − b 1/3 0 √ −b( 2/3) 0 0 0 0 0 0 α1 + b( 1/3) 0 √ −b( 2/3(1)) 0 0 0 0 √ −b 2/3 0 α1 − b( 2/3) 0 0 0 0 0 0 √ −b 2/3 0 α1 + b( 2/3) 0 0 0 0 0 0 0 0 α1 + b(−2) 0 0 0 0 0 0 0 0 α1 + b(2) Next we ﬁnd the eigenvalues ∆i . − . 0 | .1 Variational method Formalism Let’s think about that helium calculation again. = | 1. 2 2 2 2 2 3 3 1 1 1 = | . 1. 1.|4 |5 |6 |7 |8 1 1 1 1 1 1 =− | 1. + = | . + 2 2 2 3 2 2 1 1 1 3 3 = | 1. 2 2 2 2 2 1 1 1 | 1. Then we included the interaction of the two electrons as a perturbation. 0 | . − + 3 2 2 2 1 1 | 1. − = | . The energy of the state | i shifts by ∆i . 3 2 2 3 1 2 1 1 1 = | . = | 1. −1 | . . 1. = 2 2 2 2 1 1 | 1. 3 3. − 3 2 2 1 1 1 | 1. 1 | . . 1. 1 | . . 1 | . We approximated the wave function for the Helium atom with two electrons as the product of the wave functions of two singly ionized atoms. − . −1 | . 18 . 1. 2 2 2 3 2 2 3 1 1 = | . 0 | .

That is. each electron does not really see the full coulomb attraction because it is shielded by the other. So why not try to come up with a better approximation. The approximate wave function is | ψ1 | ψ2 = Then we calculated 0 0 Eapprox = E1 + E2 + ∆ = ψ1 ψ2 | H | ψ1 ψ2 = ψ1 ψ2 | H0 | ψ1 ψ2 + ψ1 ψ2 | HH | ψ1 ψ2 Z3 πa3 0 1/2 Z3 πa3 0 1/2 e−Zr1 /a0 e−Zr2 /a0 Now it is possible to write our trial wave function as a linear combination of the complete set of exact eigenkets. The eﬀective Z is a little less than 2. It’s expectation value will always overestimate the ground state energy. H| n = En | n Then Eapprox = n |an |2 En ≥ E0 n |an |2 So we know for sure that Eapprox ≥ E0 and in fact that will be true for any trial wave function that we choose. Now we compute ψ1 ψ2 | H | ψ1 ψ2 = ψ1 ψ2 | p2 | ψ1 ψ2 2m + ψ1 ψ2 | −Ze2 −Ze2 + | ψ1 ψ2 r1 r2 + ψ1 ψ2 | e2 | ψ1 ψ2 |r1 − r2 | 19 . | ψ1 ψ2 = n an | n . One adjustment that we might make is to account for the shielding eﬀect of one electron on the other. This is very important.The total hamiltonian is H= p2 p2 e2 Ze2 Ze2 1 + 2 − + − 2m r1 2m r2 |r1 − r2 | with Z = 2. We can incorporate this approximation in our wave function by writing | ψ1 | ψ2 = Z3 πa3 0 1/2 Z3 πa3 0 1/2 e−Z r1 /a0 e−Z r2 /a0 = Z πa0 3 e−Z (r1 +r2 )/a0 Or deﬁne a0 = a0 /Z and we get that ψ1 ψ2 = 1 πa 3 1/2 e−r/a 1 πa 3 1/2 e−r/a Note that our new wave function is normalized.

Set dH 5 5 27 = (2Z − 2Z + ) = 0 → Z = Z − = dZ 8 16 16 And H = −2. This is OK because no matter what we choose for Z . we minimize the expectation value with respect to Z .Note that ψ1 and ψ2 just look like the hydrogen ground state.1 Time dependent perturbation theory Formalism Now e want to consider time dependent perturbations. Next. Typically the time dependent part of the hamiltonian is something that turns on and then oﬀ so it is reasonable to ask about the probability of 20 . namely | n and as usual H0 | n = En | n .2 Examples 4 4. Therefore ψ1 ψ2 | The second term ψ1 ψ2 | −Ze2 −Ze2 + | ψ1 ψ2 r1 r2 = −2Z e2 a = −2 Z Ze2 a0 p2 | ψ1 ψ2 2m =2 Z e2 2a = Z 2 e2 a0 The third term we calculated before E 1 = e2 Therefore ψ1 ψ2 | H | ψ1 ψ2 = (Z − 2Z Z + Z 2 Z3 πa3 2 e−2Z (r1 +r2 )/a 2 2 r1 + r2 − 2r1 r2 cos θ2 2 2 r1 dΩ1 r2 dΩ2 = e2 5 e2 5 =Z 8a 8 a0 5 e2 ) 8 a0 It will be a function of the parameter Z .5ev a0 3. The Hamiltonian is written in the form H = H0 + V (t) We suppose that we know the complete set of eigenkets of H0 . we know that we are overestimating the energy. the time evolution h operator is not simply e−iHt/¯ . We note that for a time dependent hamiltonian.85 e2 = −77.

t0 . And we attach the time dependence from the perturbation to the states. t Observables are h h AI = eiH0 t/¯ As e−iH0 t/¯ I h = eiH0 t/¯ | α. t0 . An arbitrary state at t = 0 can be written |α = cn (0)| n n We want | α. t0 . t0 . t I h ∂t ∂ i¯ | α. t0 . t S I ∂ h e−iH0 t/¯ | α. t = VI | α. t . t0 . t0 . t0 . t = n h cn (t)e−iEn t/¯ | n We work in the interaction picture. t m I (16) Also from Equation 15 we see that cn = n | α. t0 .ﬁnding the system in one of the uperturbed states. So in the interaction picture | α. t0 . t = ∂t n | VI | m m | α. t0 . t = eiH0 t V e−iH0 t | α. t I ∂t h ∂ i¯ e−iH0 t/¯ | α. and the Heisenberg picture in which the states are ﬁxed and the operators evolve. t0 = 0. t S According to the Schrodinger equation i¯ h i¯ h ∂ | α. t I h ∂t h = (H0 + V )e−iH0 t/¯ | α. t0 . Then i¯ h where ωmn = d cn (t) = dt Vnm eiωnm t cm (t) m En − Em h ¯ 21 . t = n cn (t)| n (15) Substitute that last into Equation 14 and multiply from the left by n | and we have i¯ h ∂ n | α. t0 . in which operators have no time dependence. we take the time dependence associated with the unperturbed Hamiltonian from states and attach it to operators. t ∂t S = (H0 + V )| α. but the states evolve in time. which is somewhere between the Schrodinger picture. t0 . In the interaction picture. t I I (14) Then we can also write that | α.

1. t0 . t0 . t0 iH0 t/¯ h U (t. VI (t ) + t0 −i h ¯ dt t0 t0 dt VI (t )VI (t ) 4. t0 )dt t0 2 t t dt i h ¯ = +. t0 ) = 1 − = 1− i h ¯ t VI (t ) 1 − t0 t i h ¯ t VI (t )UI (t . t0 ) = 1 − i h ¯ t I = UI (t.1 Transition Suppose we have a system in an eigenket | i . t0 . t = UI (t. We note that |i |i |i I I I h = eiH0 t/¯ | α. t0 )|t=t0 = 1 and we integrate to get UI (t. t0 . t0 )| i = n | n n | UI (t. t0 )dt t0 We get an approximate solution by iteration: UI (t. t0 ) dt VI (t )UI (t . t0 )| α. t0 ) | i = n cn (t) We see that n | UI | i is the amplitude that a system initial in state | i will be in state | n as a function of time. t i¯ h The initial condition is U (t. t0 )| α. t S S I = e = e iH0 t/¯ h U (t. Then | i. t0 )e−iH0 t0 | α. t0 . t0 ) = eiH0 t/¯ US e−iH0 t0 /¯ Therefore h n | UI | i = ei(En t−Ei t0 )/¯ n | U | i 22 .. t0 . t0 ) = VI (t)UI (t. t0 h h → UI (t. t0 I d UI (t..and we used h h h n | eiH0 t/¯ V (t)e−iH0 t/¯ | m = Vnm (t)ei(En −Em )t/¯ We expand the time evolution operator | α.

more or less nearby we replace |cn |2 → dEρ(En )|cn |2 = 4 sin2 2 (En − Ei )t |Vni ρ(E)dE 2¯ h |En − Ei |2 Next we see that t→∞ lim sin2 (En − Ei )t |Vni |2 πt ρ(E) = δ(En − Ei ) 2 2¯ h |En − Ei | 2¯ h 23 .2 Constant perturbation We turn on a constant perturbation at t0 . n.1. | n | UI | i | = | n | U | i | So c0 (t) = δni n i c1 (t) = − n ¯ h i c1 (t) = − n ¯ h c2 (t) = n = − − i h ¯ i h ¯ t n | VI (t ) | i dt t0 t t0 2 m 2 m t t h n | V (t ) | i ei(En −Ei )t/¯ dt dt t0 t t0 t dt n | VI (t ) | m m | VI (t ) | i dt t0 t0 dt Vnm (t )eiωnm t Vmi (t )eiωmi t 4.En =Ei and if there are many ﬁnal states.Then as long as keti and | n are eigenkets of H0 . Then the amplitude to make a transition from state i to n to ﬁrst order is cn (t) = − Then |cn (t)|2 = 4 |Vni |2 |Vni |2 |Vni |2 sin2 (ωni t/2) = 4 sin2 (ωni t/2) = 4 sin2 ((En − Ei )t/2¯ )2 h (En − Ei )2 (En − Ei )2 h 2 ¯ 2 ωni i h ¯ t t0 Vni eiωni t = −i Vni eiωni t − 1 h ¯ iωni If En = Ei . then |cn (t)|2 = ¯12 |Vni |2 t2 If there is a ﬁnite number of ﬁnal states close to h | n then the total transition probability is |cn |2 .

3 Second order perturbation We found earlier that c2 (t) = − n 1 h ¯2 t t dt m 0 0 dt Vnm (t )eiωnm t Vmi (t )eiωmi t If V (t) is constant in time then c2 (t) = − n t 1 eiωmi t − 1 dt Vnm eiωnm t Vmi iωmi h ¯2 m 0 t 1 1 dt Vnm eiωni t − eiωmn t Vmi = − 2 iωmi h ¯ m 0 t i Vnm Vmi eiωni t − eiωmn t dt = h ¯ m Em − Ei 0 ∼ i h ¯ m Vnm Vmi Em − Ei t 0 eiωni t dt Now it looks just like the ﬁrst order term with −i i Vni → h ¯ h ¯ So to second order wi→n 2π = Vni + h ¯ Vnm Vmi 2π ρ(En ) → Ei − Em h ¯ 2 m Vnm Vni Em − Ei dEn Vni + m m Vnm Vmi ρ(En )δ(En − Ei ) Ei − Em 2 The average is over all ﬁnal states n with energy En ∼ Ei . 4.1.Finally |cn (t)|2 = The rate is wi→n = or wi→n = ρ(E)dE|cn (t)|2 = 2π |Vni |2 ρ(En )t h ¯ 2π |Vni |2 ρ(En ) h ¯ 2π |Vni |2 δ(En − Ei ) h ¯ where integration over ﬁnal states is implied. 24 .

In our study of time dependent perturbation theory we determined the the transition probability from initial state ψa to ﬁnal state ψb is given by the absolute square of the amplitude cb (t) = − i h ¯ t/2 −t/2 ψb | H(t ) | ψa eiωab t dt where ωab = Ea −Eb . Then we can integrate and we get cb (t) = − Hab 2i sin ωab t/2 i 1 eiωab t/2 − e−iωab t/2 Hab = − h ¯ iωab h ¯ ωab 2 1 1 sin ωab t/2 2 4 sin ωab t/2 = 2 |Hab |2 2 2 |Hab | ωab t/2 ωab h ¯ h ¯ 2 and the transition probability is |cb |2 = t2 Let’s examine the ωab dependent piece f (ω) ≡ sin ωt/2 ωt/2 2 t2 The ﬁrst zero of f (ω) occurs when ω = 2π/t.4 Scattering Scattering from a ﬁxed potential is a ﬁne example of a perturbation that turns on. the detector always has some ﬁnite acceptance. Its maximum value (at ω = 0) is t2 . 2πtδ(ω) → 2πt¯ δ(Eb − Ea ) h and we can write |cb |2 = The transition rate is R= 1 |Hab |2 2πtδ(Eb − Ez ) h ¯2 2π |Hab |2 δ(Eb − Ea ) h ¯ In scattering experiments. To apply the theory to a scattering process we imagine that the h ¯ perturbation H(t ) turns on at −t/2 and oﬀ at t/2 and while it is turned on it has constant value H. R= 2π h ¯ |Hab |2 δ(Eb − Ea )ρ(Eb )dEb 25 . f (ω) → 2πtδ(ω). In the limit of large t.1. To check that assertion we integrate over all ω ∞ f (ω)dω = −∞ sin2 x 2 2 dx t = 2πt = x2 t 2πtδ(ω)dω In terms of the energies of initial and ﬁnal states. And what we measure is a sum over all ﬁnal states consistent with that acceptance. stays on for awhile and then turns oﬀ.4.

And V (dσ)Flux = dN = R dσ = R V 2 m2 = | ψb | H | ψa |2 dΩ Flux (2π¯ 2 )2 h dσ = dΩ That means that f (θ) = − Vm 2π¯ 2 h 2 |Hab |2 mV ψb | H | ψa 2π¯ 2 h The negative sign is a convention. Well. we have ﬁgured this out before. the number of ﬁnal states per unit energy.ρ(Eb ) is the density of ﬁnal states. The number of states between k and k + dk is dN = V k 2 dkdΩ V p2 dpdΩ = 8π 3 (2π¯ )3 h Using E = p2 /2m and 2pdp/2m = dE we have dN = V pmdEdΩ (2π¯ )3 h dN V pm = ρ(E) = dΩ dE (2π¯ )3 h so R= 2π 1 V pm|Hab |2 dΩ h ¯ (2π¯ )3 h Now how do we connect to the cross section? The incoming particle is represented by a plane wave 1 ψa = √ eika ·r V and the outgoing wave by 1 ψb = √ eikb ·r V √ The V in the denominator is so that the wave function is normalized. Then f (θ) = − mV 2π¯ 2 h m = − 2π¯ 2 h 1 1 √ e−ikb ·r V (r) √ eika ·r d3 r V V ei(ka −kb )·r V (r)d3 r The result is equivalent to that of the Green’s function analysis in the ﬁrst Born approximation. The particle density v in the incoming wave is |ψa |2 = 1/V and the ﬂux of incoming particles is V = p/m . 368) 26 . (See Griﬃths p. Suppose that H = V (r).

2 Harmonic perturbation V (t) = V eiωt + V † e−iωt Now suppose that the perturbation is We will get that cn (t) = − i t † Vni ei(ωni +ω)t + Vni ei(ωni −ω)t h ¯ 0 i(ωni −ω)t − 1 i ei(ωni +ω)t − 1 † e = − Vni + Vni h ¯ i(ωni + ω) i(ωni − ω) If ωni ∼ ω then the second term is the signiﬁcant one. The typical transition energy for an atom is Z 2 e2 E< 2a0 27 .) In the long wavelength limit. Then A ∼ 2A0 (1 + ik · x + . Then |cn (t)|2 = 4 4π sin2 (ωni ± ω)t/2 = lim → 2 |Vni |2 δ(ωni ± ω)t/2 |Vni |2 2 2 t→∞ (ωni ± ω) h ¯ h ¯ and just like for the constant perturbation wi→n = π2 2π 2 2 h 2 |Vni | πδ(ωni ± ω) = ¯ |Vni | δ(En − Ei ± ¯ ω) h h ¯ En = Ei ± ¯ ω h 4. . En > Ei and there is absorption. Small that is compared to the size of the wave function which is perhaps the size of an atom. . We can expand the exponential for small k. For that very V (t) = − ei(ωt−k·x) + e−i(ωt−k·x) legit as long as same plane wave A = 2A0 cos(ωt − k · x) = A0 Consider absorption.2. xk → 2πx/λ is small. Then we take the second term.1 Let Interactions with radiation ﬁeld e A·p mc · A = 0 which is true for a plane wave in empty space. If Ef < Ei then ωni < 0 and the ﬁrst term counts.4.

we can replace ρ with an expression for the density of ﬁnal states available to the photon.3 Spontaneous emission An alternative strategy for determining the spontaneous emission rate is to begin with the expression for the stimulated rate.The corresponding wavelength is λ∼ h ¯c 2a0 2a0 ¯ c h = 2 2 = 2 E Z e Z α a0 The transition rate in the dipole approximation is wi→n = 2π e | A0 n | · p | i |2 δ(En − Ei ± ¯ ω) h h ¯ mc 1 2 2 Emax 8π The energy density of the radiation ﬁeld is U = gives us wi→n = → = = = = = In the last step we use n | [H.2. x] | i | h h ¯ (2πe)2 ρ(ω)| · n | x | i |2 h ¯2 −¯ h n | p | i = hωni n | x | i ¯ m 4. x] | i = + 2 Bmax 8π = 1 ω2 2 2π c2 |A0 | .2. 4. In the event of spontaneous emission. Substitution (2π)2 e U| n | · p | i |2 δ(En − Ei ± ¯ ω) h h ¯ mω e (2π)2 ρ(ω)dω| n | · p | i |2 δ(En − Ei ± ¯ ω) h h ¯ mω (2π)2 e 2 2 ρ(ω)| mω n | · p | i | h ¯ e (2π)2 2 2 ρ(ω)| mω · n | p | i | h ¯ e m (2π)2 2 2 ρ(ω)| mω ¯ · n | [H. Let’s try to come up with a more systematic development.2 Absorption vs emission The rate that we just computed for absorption from a radiation ﬁeld with energy density ρ(ω) is identically the rate we would ﬁnd for the emission in that same radiation ﬁeld. 28 . and then substitute the ground state radiation density of the vacuum.

We get wi→n = 2π h ¯2 2πc2 ρ(ωni ) ω2 e mc 2 | n | · peik·r | i |2 What do we mean by ρ(ω)? It is the energy density per unity volume per unit frequency. etc. The total number of states with energy E < ¯ kc. We simply replace the expression for the radiation density with the energy density of available photon states. But we can develop an expression for spontaneous emission based on a heuristic argument. How do we get from here to spontaneous emission? It must be that there is some vacuum ﬂuctuation or vacuum radiation density. The transition rate from n → i or in the other direction is exactly the same. We use U= Then wi→n = 2π h ¯ 2πc2 U ω2 2 1 ω2 |A0 |2 2π c2 | n | · peik·r | i |2 δ(En − Ei ± ¯ ω) h e mc U has some frequency dependence. We need second quantization for a mathematically complete theory. is h N = = = 1 dN V dω = 14 π(n2 + n2 + n2 )3/2 x y z 83 14 L 3 2 3/2 π (k ) 83 π π L 3 ω 3 ( ) 6 π c 2 1 ω number of states per unit volume per unit frequency 2π 2 c3 29 . The density at the frequency corresponding to the transition energy is the only part that counts. The total energy density is ρ(ω)dω = U We replace U with ρ(ω)dω and integrate with the δ function. in one case it is absorption and in the other it is stimulated emission. where kx = πnx /L.The rate wi→n = 2π h ¯ e A0 mc 2 | n | · peik·r | i |2 δ(En − Ei ± ¯ ω) h We want to replace vector potential with energy density.

φ = 0. So project onto the x-axis.4 Average over polarization and angle To get the total spontaneous emission rate we average that last over all directions k for the outgoing photon and all polarizations . the energy of the photon in the state and we end up with h ρ(ω) = The spontaneous transition rate becomes wi→n = 4π ¯2 h h 2πc2 ¯ ω 3 2 2π 2 c3 ω ω ¯c h e mc 2 h ¯ ω3 π 2 c3 | n | · peik·r | i |2 e 2 | n | · peik·r | i |2 mc α 1 = 4 (ω) | n | · peik·r | i |2 mc2 m = 4 which sure enough is a rate. Then the polarization is in the y-z plane and the average of 1 1 · ˆ 2 = 4π sin2 sin θdθ cos2 αdα = 4π ( 4 )π = 1 . then · x = 0.5 Angular distribution Suppose we know that the transition is E1 and ∆m = 1. The total spontaneous decay rate into z 3 3 all angles and polarizations is wi→n = 4 3 α ω | n | x | i |2 3 c2 4.2.2. Suppose that x is along the z-direction and the outgoing photon is at an angle θ. First note that if θ = 0. In the dipole approximation we get wi→n = 4 (ω) α 1 |mω n | · x | i |2 mc2 m α = 4 ω 3 2 | n | · x | i |2 c 4.Finally to get the energy density we multiply by two to include the two polarization states and multiply by ¯ ω. Then f | x | i = l ± 1. m ± 1 | x | lm 30 . Since it is E1 that means that ∆l = ±1 by Wigner Eckart.

3 Photo electric eﬀect Imagine a hydrogen atom at rest at the origin. Then the rate is the incoming ﬂux times the cross section. No z-component. φ) direction with momentum p = hkf ¯ 31 . The incoming energy ﬂux is the energy density times the velocity. we could deﬁne the cross section. Electromagnetic radiation in the form of a plane wave is propagating in the +z direction (k = |k|ˆ) with E-ﬁeld polarized along z the x-direction. We get all of the z-direction piece and half of the x-direction piece so the probability to go into the angle θ is P (θ) = cos2 θ + which happens to be the same |d1 |2 + |d1 |2 = 1. The electron ﬂys oﬀ in the (θ. The ﬂux of photons is the energy ﬂux/photon energy.6 Absorption cross section Or instead of writing the rate in terms of the energy density of the incident radiation. The radiation ﬁeld interacts with the atom and frees the electron. The angle θ is that of the polarization with respect to the y-axis.will be a vector in the x-y plane.−1 1 (1 + cos θ) 2 2 1 1 sin2 θ = (1 + cos2 θ) 2 2 2 + 1 (1 − cos θ) 2 1 = (1 + cos2 θ) 2 4.2. x] and get that h σabs = σabs = (2π)2 ωe2 (2π)2 ωe2 | n | · x | i |2 δ(En − Ei ± ¯ ω) = h | n | · x | i |2 δ(ωni − ω) c ¯2 c h ¯ h If we suppose the polarization is in the x direction then The total absorption cross section is σ(ω)dω = 4π 2 ωni α| n | x | i |2 n 4. If it is headed in the x-direction then we need to average. That means that if the photon is headed in the z-direction · x = 1 for all polarizations.1 1. it has a component cos θ in the z-direction and and component sin θ in the x-direction. So Rate = σFlux Then and Flux = cU/¯ ω h wi→n ¯ ω h (2π)2 e2 = | n | · p | i |2 δ(En − Ei ± ¯ ω) h cU c m2 ω Again we replace p with m/¯ [H. 1 2π cos2 θdθ = 1 2 For a photon headed in the θ direction with respect to the z-axis.

We assume that the energy of the electron is so high that we can neglect the eﬀect of the coulomb attraction of the hydrogen nucleus in the ﬁnal state.3. We imagine the plane wave in a box with sides of length L so that it is normalized over the volume.3.4. A = 2A0 cos(k · r − ωt) = A0 e i(k·r−ωt) The interaction hamiltonian is (17) (18) +e −i(k·r−ωt) where is the unit vector that gives the polarization of A and E = − ∂A After application ∂t of the energy conserving δ-function we are left with A = A0 ei(k·r−ωt) Then H = −i¯ q h A0 eik·r · mc 32 .1 Golden rule The transition rate is given by the golden rule R= | f | H | i |2 2πδ(Ef − Ei − ¯ ω) h h ¯ The initial state is the ground state of hydrogen 2 e−r/a x|i = √ 4πa3 The ﬁnal state is a free electron x|f = 1 L3/2 eikf ·r which we represent as a plane wave. 4.2 Interaction Hamiltonian H = q A·p mc We write the vector potential as a plane wave.

φ into solid angle dΩ. The total number of states with |k| < |kf | is x y z 3/2 4 4 N = π(n2 + n2 + n2 )3/2 = π x y z 3 3 The number of states per unit k into solid angle dΩ are dN 4 L = π dk 3 2π 3 L k 2π 2 3k 2 dΩ 4π The number of states per unit energy into solid angle dΩ are dN dE = = where we have use E = h ¯ 2 k2 2m . L 2π L 2π 3 k2 3 dk dΩ dE 4π km dΩ h ¯2 (19) (20) 4.3 Density of states The free electron in the ﬁnal state is traveling at angle θ.4 Transition rate | f | H | i |2 2π δ(Ef h ¯ | f | H | i |2 L 3 2π = h ¯ 2π 2 qA0 = ¯ h | f | eik·r · mc The total transition rate is R = − Ei − ¯ ω) h km dΩ ¯2 h | i |2 2π L 2π 3 dN dE (21) (22) km dΩ h ¯2 (23) 33 .3. n2 + n2 + n2 . ky = .3. In order to determine the total rate for the transition we need to integrate over all possible ﬁnal state electrons that are directed into the solid angle. kz = L L L 2π L 2 (n2 + n2 + n2 ) x y z Imagine a sphere of radius the volume of the sphere. The electron wave function at the boundaries vanishes so kx = and 2 kf = 2nx π 2ny π 2nz π .4. The electrons are free particles conﬁned to a box with side L.

We are assuming that the energy of the ﬁnal state electron is big compared to the binding energy.5 Absorption cross section dσ Rate for photoelectrons = dΩ Flux of incident photons We deﬁne a diﬀerential cross section The energy ﬂux for the incoming plane wave is cu = c 2 1 ω2 2 Emax = A 8π 2π c 0 and since each photon has energy ¯ ω. the photon ﬂux is h Flux = Then dσ dΩ = h ¯ (mc)02 | f | eik·r · 2π(q¯ )2 | f | eik·r · h = q 2 | f | eik·r · = 2πmcω q 2 A2 1 1 ω 2 A2 = ωA2 0 0 2π¯ ωc h 2π¯ c h 3 | i |2 2π | i |2 2π L 2π km h ¯2 3 (ωA2 /2π¯ c) h 0 L 2π km h ¯2 (24) m2 cω | i |2 L3 k (25) (26) 4. We have that 1 1 f | eik·r · | i = 3/2 1/2 3/2 I L π a where I = e−ikf ·r eik·r · e−r/a r2 drdΩ Integrating by parts we get that I = − − · · · e−ikf ·r eik·r e−r/a r2 drdΩ e−ikf ·r eik·r e−r/a r2 drdΩ e−ikf ·r eik·r e−r/a r2 drdΩ (27) (28) (29) 34 .3.6 Expectation value All that remains is to compute the expectation value.4.3. Therefore it is not safe to assume that k · r 1 and we will attempt to do the integral exactly. Note that it is not appropriate to work in the electric dipole limit.

Equation 11 can be written as a surface integral over a volume that we can take to inﬁnity. The wave function falls oﬀ exponentially so Equation 27 is zero. First we do the angular integral I = i2π · kf Then integrate over r. I = 2π · kf = 2π = 2π = 2π = 2π Finally f | eik·r · |i = = 1 L3/2 1 π 1/2 a3/2 2π · kf a(q 2 −4i + (1/a)2 )2 (41) (42) (43) (e−iqr−r/a − eiqr−r/a ) rdr iq 1 1 · kf − 2 q(−iq − 1/a) q(iq − 1/a)2 1 1 · kf − 2 + 1/a2 − 2iq/a) 2 + 1/a2 + 2iq/a) q(−q q(−q −4iq/a · kf 2 + 1/a2 )2 + 4(q/a)2 )2 q((−q −4i · kf 2 + (1/a)2 ) a(q (36) (37) (38) (39) (40) (e−iqr − eiqr ) −r/a 2 e r dr iqr (35) −8iπ 1/2 · kf L3/2 a3/2 a(q 2 + (1/a)2 )2 35 . Finally I = · eikf ·r eik·r e−r/a r2 drdΩ e−ikf ·r eik·r e−r/a r2 drdΩ e−i(kf −k)·r e−r/a r2 drdΩ e−iq·r e−r/a r2 drdΩ e−iq cos θr e−r/a r2 dr sin θdφ (30) (31) (32) (33) (34) = −i · kf = −i · kf = −i · kf = −i · kf where q = kf − k. On taking the gradient Equation 29 and pulling k outside of the integral. we get i ·k since polarization e−ikf ·r eik·r e−r/a r2 drdΩ = 0 and propagation vector k are orthogonal.

3. Then q 2 = kf + k 2 − 2kf k cos θ.and dσ dΩ = = α¯ L3 kf h 2πmω 8π 1/2 · kf L3/2 a5/2 (q 2 + (1/a)2 )2 2 (44) (45) 32α¯ kf h ( · kf )2 mω a5 (q 2 + (1/a)2 )4 4. φ = 0 direction. φ direction. namely parallel to the polarization of the ﬁeld. And the polarization is in the x-direction so that · kf = kf sin θ cos φ and 32α¯ kf h (kf sin θ cos φ)2 dσ == 2 dΩ mω a5 (kf + k 2 − 2kf k cos θ + (1/a)2 )4 The diﬀerential cross section is peaked for the outgoing electron in the θ = π/2. 36 .7 Angular distribution The E-ﬁeld vector k is in the z-direction and the electron in the ﬁnal state has kf in the 2 θ.

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