Physics 4 - Quantum Physics 2000-1 - Answers.

These answers are intended to reassure that you have got the problems right. They are
not model solutions, and would be unacceptably terse as examination solutions.
1 Perturbation and Matrix Elements
For integer n:
1

a
cos
(2n + 1)x
2a
;
1

a
sin
2nx
2a
For perturbation theory va should be much smaller than the dierence between energy levels of dierent
n:
va <<
(2n + 1)
2
h
2
8ma
2
First order energy shift: n|vx|n = 0.
Matrix elements, by symmetry, integer n,m: 2m|vx|2n = 2m+ 1|vx|2n + 1 = 0
For n odd, m even:
V
nm
=
4av

2
_
/2
/2
y cos(ny) sin(my)dy e.g. V
12
=
32va
9
2
267|vx|387 = m|vx|m+ 738 = 0
2 Completeness and Orthonormality in Vectors
Consider a unit vector a = (1, 1, 3)/

11. What are its components (dot products) in the following

basis sets u
i
:
a) 1/

11, 1/

11, 3/

11: complete, orthogonal, normalised

b) (

3 + 1)/2

11, (1

3)/2

11: incomplete, orthogonal, normalised

c) (

3 + 3)/2

11, (

3 + 3)/2

11, 1/

11: complete, non-orthogonal, normalised

d) (

3 + 3)/2

11, (1 3

3)/2

11, 1/

11: complete, orthogonal, normalised

e) 0, 7/

11, 6/

11: complete, orthogonal, unnormalised

f) (3

3)/2

11, (1 + 3

3)/2

11, 1/

11, 0. overcomplete, non-orthogonal, unnormalised

g)

2/

11, 3/

11: incomplete, orthogonal, normalised

h) (1 +

3)/2

11, (1

3)/2

11,

2/

11: incomplete, non-orthogonal, normalised

Complete, orthogonal and normalised i for any a:

i
|u
i
a|
2
= 1 and u
i
u
j
=
ij
The Fourier series is orthogonal and tends to completeness as k . Atomic orbitals centred on
dierent sites are not orthogonal and may become overcomplete. Thus Fourier series have an advantage
in completeness. However, the bonding orbitals in H
2
are more similar to the atomic ones, and a basis
set of just two 1s wavefunctions gives as good a description of the bonding as could hundreds of Fourier
components.
1
3 One electron atoms
a)
nl0
|v

l
z
|
nl0
= 0; ;
211
|v

l
z
|
211
= v h; ;
211
|v

l
z
|
211
= v h;
b)
100
|vr
2
|
100
= 3v(a
0
/Z)
2
;
200
|vr
2
|
200
= 42v(a
0
/Z)
2
;
210
|vr
2
|
210
= 30v(a
0
/Z)
2
;

211
|vr
2
|
211
= 30v(a
0
/Z)
2
c)
100
|vr|
100
= 1 5v(a
0
/Z) ;
200
|vr|
200
= 6v(a
0
/Z) ;
210
|vr|
210
= 2 5v(a
0
/Z) ;

211
|vr|
211
= 2 5v(a
0
/Z)
d)
100
|ve
2r/a
0
|
100
= v(
Z
Z+1
)
3
;
200
|ve
2r/a
0
|
200
= vZ
3
[(
1
Z+2
)
3
+ (
3Z
2
(Z+2)
5
+
3Z
(Z+2)
4
] ;

21m
|ve
2r/a
0
|
21m
= fracv2(
Z
Z+2
)
5
;
e)
100
|ve
Zr/a
0
|
100
=
8v
27
;
200
|ve
Zr/a
0
|
200
=
v
32
;
21m
|ve
Zr/a
0
|
21m
=
v
64
Notice that all o-diagonal terms with the same n are zero: none of these perturbations mix the
eigenstates. (a) actually commutes with the Hamiltonian, so doesnt mix n=1 with n=2 states, in this
case the energy shifts are exact for any v. (b-e) mix states of n=1 and n=2, and so perturbation is
only correct when the matrix element is much less than the energy dierence between the n=1 and n=2
states (0.75Z
2
Ryd.).
4 Commutation
i h, 0, 0, i hz, 0, i h p
z
, i h

l
z
5 Spin-Orbit Coupling

j
2
= (

l +s)
2
=

l
2
+2

l s +s
2

l s =
1
2
[

j
2

l
2
s
2
]
For 1s and 2s, E = 0
For 2p, fourfold degenerate, J =
3
2
, E = /2
For 2p, twofold degenerate, J =
1
2
, E =
First order because we assume the perturbed wavefunctions are the same as the hydrogen ones. Degen-
eracy is only partly lifted because there is still symmetry with respect to rotating the atom. Note that
four levels are raised by /2 while two are lowered by : the average energy of a 2p state in unaected,
though in fact each atom will be in one state or the other, so this is not a conservation law.
6 Degenerate Perturbation
Other orthogonal state: cos( +

2
)|
1
+ sin( +

2
)|
2
.

2
|

V |
1
= V
1
since operator must be Hermitian. Eigenvalues of the matrix are V
0
V
1
, so splitting
between levels is 2V
1
. Eigenstates correspond to = /4.
Initial state is |
1
. When

V is applied it collapses onto |(/4). For both of these states |(/4)|
2
|
2
=
1
2
, thus the probability of measuring |
2
when the perturbation is removed is
1
2
.
Time dependent perturbation theory would be inappropriate because the perturbation is larger than
the energy dierence between the unperturbed states (which is zero).
7 Good quantum numbers in hydrogen
b), e) and j) are good sets. a) is not good since L
z
and L
x
do not commute. d) is not good since x does
not commute with the other operators. c), g), h), i) and j) do not give dierent labels to |200 and
|210 . f) does not give dierent labels to |211 and |210 .
2
8 Periodic perturbation
Energy of

is h
2
k
2
/2m and they are eigenfunctions of

H
0
.
Momentum of

is hk and they are eigenfunctions of p.

+
|

V (x)|
+
=

V (x)|

= 0

+
|

V (x)|

V (x)|
+
= 0 unless 2Lk = N
Think about what this means - to rst order, a free electron travelling through a periodic potential
(e.g. a crystal) is not aected by that potential! This is why the free electron theory of metals works
reasonably well.
If 2Lk = N then :
+
|

V (x)|

V (x)|
+
= V
0
/2
Appropriate states are (
+

)/

2, which are still eigenfunctions of H

0
but not of p.
This analysis is similar to the opening of a band gap by a periodic potential in solid state band theory
of a one dimensional crystal.
The non-zero matrix element from combining terms on either side of |k| = N/2L is
_
L
0
exp[i(N +)x/2L]v
o
cos(2kx) exp[i(N )x/2L]dx = L/2
Thus the second order energy shift of the state at |k| = N/2L is:
E =
(v
o
L/2)
2
h
2
2N/8mL
2
=
mv
2
0
N h
2

i.e. its energy is reduced. Even second order perturbation breaks down as 0 (because the unper-
turbed states are closer together in energy than the size of the perturbation), but we do know the exact
limit to which the energy shift should tend from the degenerate result above.
9 Stark Eect
There are 81 elements, of which 73 are zero. Of the remaining eight, there are four equal pairs
300|z|310, 320|z|310 and 32 1|z|31 1, and in fact only two are distinct since 320|z|310
= 32 1|z|31 1.
Dening a = 300|z|310 and b = 320|z|310, we can block diagonalise the matrix and nd the
eigenvalues:

_
(a
2
+b
2
), 0 ,
_
(a
2
+b
2
), b, -b, b, -b, 0 , 0.
10 Neutral kaons
CP|K
0
= |K
0
; CP|K
0
= |K
0

Consider a general state | = a

0
|K
0
+b
0
|K
0

The total intensity is proportional to | = |a

0
|
2
+|b
0
|
2
, of which |a
0
|
2
are K
0
s. And
3
|
1
2
(

S + 1)| = |a
0
|
2
Similarly, the intensity of K
0
is |b
0
|
2
and comes from the expectation value of
1
2
(1

S)
If we assume K
0
intensity I
K
0(t) = |a
0
(t)|
2
, then.
|a
0
(t)|
2
=
1
2
(

S + 1) =
1
4
|a
0
(0)|
2
_
e
t/
1
+e
t/
2
+ 2e
t/2
1
e
t/2
2
cos(m
12
t)
_

S = |a
0
(0)|
2
e
t/2
1
e
t/2
2
cos(m
12
t)

S
2
=
1
2
|a
0
(0)|
2
_
e
t/
1
+e
t/
2
_

1
2
(

CP + 1) =
1
2
|a
0
(0)|
2
e
t/
1

CP =
1
2
|a
0
(0)|
2
_
e
t/
1
e
t/
2
_
Leaving the matter, the appropriate collapsed eigenstates are |K
0
and |K
0

The nal kaon intensity is a quarter of the initial intensity. Had the matter not intervened, the nal
kaon intensity would have been half of the initial intensity.
11 Variational principle
a) a
2
=

2
6
12
m
h
;

H
0
= 0.568 h
b) a
2
=

35
2
h
m
;

H
0
= 0.598 h
c) =
m
2 h
;

H
0
= 0.5 h
d) a
2
=

15
h
m
;

H
0
= 0.548 h
e) a
2
=

2
2
3
6
m
h
;

H
0
= 1.607 h
12 Degenerate Perturbation
Eigenstates: [sin
x
L
cos
y
2L
sin
y
L
cos
x
2L
]/L
Energy shifts =
1024
81
4
vL
2
4
13 Properties of Legendre Polynomials
_

0
P
l
(cos )P
m
(cos )d =
m
l
2
2l + 1
P
l
(1) = 1 and P
0
(0) = 1, P
2
(0) = 0, P
3
(0) =
1
2
, P
4
(0) = 0.
For the dipole, V = eEz etc. l = 1 ( integral), m
s
= 0 (spin integral), m
l
= 1, 0 ( integral)
For the quadrupole, V = eExy etc. l = 2, 0 ( integral), m
s
= 0 (spin integral), m
l
= 2, 1, 0
( integral)
14 Abstract Operators

Q =
_
1 0
0 0
_
The eigenvectors are just |p = [1 0] and |n = [0 1], the eigenvalues are 1 and -1

T
1
=
_
0 1
1 0
_
eigenstates of

T
1
are [
_
1
2
,
_
1
2
] and [
_
1
2
,
_
1
2
] both with charge expectation values of
1
2
15 Density of states - Born Approximation
States between E and E+dE:
mkL
3
2 h
2

2
dE
States between E and E+dE and angle between and +d:
mkL
3
4 h
2

2
sin ddE
16 Impact Parameters
Impact parameter for 1eV p-electron: 2.75

A
17 Partial Waves
According to Levinsons Theorem there are two bound states, both with l = 0.
There will be a minimum in the cross section when
0
= 2, E=1eV.
There are maxima in the cross section at
0
= 3/2: E = 1.78eV and when
1
= /2: E = 10eV .
However, the
1
= /2 maximum is coincident with the maxima from the other l-components, and thus
this is the energy with strongest scattering. The ratio of scattering strengths is 35/10 : 1/1.78 6.2
At high energy, the scattering falls as
max
/2E, since the average value of sin
2
1/2.
18 Atomic Scattering
d
d
=
m
2
e
4
4
2

2
0
h
4
[2k sin

2
]
4
[F() Z]
2
=
e
4
64
2

2
0
sin
4

2
1
m
2
v
4
[F() Z]
2
5
19 Coulomb Scattering
No Planck constant - the expression is the same as the classical Rutherford cross section.
20 Hydrogen Scattering
Redene axes for integral over all space such that polar axis is along . Use standard formula for
_
re
ar
dr with complex a.
21 Centre of mass coordinates
With M = m
1
+m
2
and = (m
1
m
2
)/(m
1
+m
2
) and total energy E = E
r
+E
R
, the equations are:

h
2
2

2
r
2
+V (r) = E
r

h
2
2M

2
R
2
= E
R

22 Imaginary Potentials
= Ae
V
1
t/ h
e
ikxiwt
+ Be
V
1
t/ h
e
ikxiwt
Is the general solution, so that | = (A
2
0
+B
2
0
)e
2V
1
t/ h
. The probability current density is then :
(
hk
m
)e
2V
1
t/ h
(B
2
0
A
2
0
)
Particles are being created. If V
1
were negative it would represent particles decaying.
23 Electron-electron scattering
(a)
d
d
= (
e
2
8
0
2E
)
2
sin
4

2
(b)
d
d
= (
e
2
8
0
2E
)
2
1
2
(sin
2

2
cos
2

2
)
2
(c)
d
d
= (
e
2
8
0
2E
)
2
1
2
_
[sin
2

2
cos
2

2
]
2
+ sin
4

2
_
6
24 Bells Theory
(a)
1
4
(b) cos
2
(
A
) cos
2
(
B
)
(c)
1
2
cos
2
(
A

B
)
(d)
1
4
(e)
1
2
cos
2 1
2
(
A

B
)
The factor of two arises because opposite-polarised photons (x and y) are at 90

while opposite spins

S
z
=
1
2
are at 180

to one another.
Hidden variables methods would give the same result for (a), (b) and (d), but will incorrectly predict
for (c)
1
4
cos
2
(
A

B
) and for (e)
1
4
cos
2 1
2
(
A

B
)
The probability averaged over all
A
and
B
is
1
4
in every case.
25 Kronig-Penney
When l = b, the equation becomes simply cos k
1
b = cos kb, whence the energy is E = h
2
k
2
/2m.
When b = 0 we have cos k
2
l = cos kl. For E > V
0
this is just the free electron again. For E < V
0
, k
2
is
imaginary, i
2
say, the equation becomes cosh
2
l = cos kl which has no solution except the trivial l=0.
The rst two cases are simply free electrons, the nal non solution shows that an electron must have at
least the potential energy of the region where it is found.
26 Hydrogen Molecular Ion
The ground state is simply one hydrogen atom and one bare proton. Since there is a choice for which
proton has the electron, it is doubly degenerate with energy E
0
. The wavefunction is simply the 1s
orbital in hydrogen. Refer to these states as |1 and |2.
The integrals are the electron wavefunction acted on by the electric eld of the other proton, premul-
tiplied either by itself or the equivalent wavefunction on the other ion. Each increases towards innity
at R=0 and drops to zero as R. V
12
is larger.
The energies of the perturbed states are:
E
0
+V
11
V
12
The electron will fall into the lower energy state E
0
+V
11
V
12
. This will produce a force between the
atoms of
dE
dR
=
dV
11
dR

dV
12
dR
since
dV
12
dR
<
dV
11
dR
, this force is attractive. (Check it using MAPLE)
The protons do not collide because of their mutual Coulombic repulsion.
The approximation comes in not including n = 2 basis functions in the wavefunction. It will break
down when V
12

3
4
R
H
, where R
H
is the Rydberg constant.
7
Some Integrals
_
a
a
(Any odd function) dx = 0
_
a
0
xcos
2
(
nx
2a
) dx =
a
2
4
_
1
4
n
2

2
_
n odd ;
_
a
0
xsin
2
(
nx
2a
) dx =
a
2
4
_
1 +
4
n
2

2
_
n odd
_
a
0
xsin
2
(
nx
2a
) dx =
_
a
0
xcos
2
(
nx
2a
) dx =
a
2
4
n even
_
/2
/2
xcos
2
xsin xdx =
4
9
_

0
x
n
exp(ax)dx = n!a
(n+1)
_
L
0
cos
2
(x/L)dx
_
L
0
sin
2
(x/L)dx = L/2
_
/a
/a
x
2
sin
2
naxdx =
(2n
2

2
3)
6n
2
a
3
;
_
/a
/a
x
2
cos
2
naxdx =
(2n
2

2
+ 3)
6n
2
a
3
_
a
a
a
4
2a
2
x
2
+x
4
dx =
16
15
a
5
_

x
2
exp(x
2
/
2
) dx =

3

2
_

exp(x
2
/
2
) dx =

_
a
0
x
2
(x a)
2
dx =
a
5
30
_
/2
/2

n=1
cos
2
nx
n
2
dx =

3
16
_

d
3
x
_

d
3
y
(x) exp (ik.y)
|x y|
=
_

d
3
x
_

d
3
z
(x) exp ik.(x +z)
|z|
=
4
k
2
_

d
3
x (x) exp ik.x
_

0
xexp(2x/a) cos(x) =
a
2
(
2
a
2
4)
(
2
a
2
+ 4)
2
8