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Physics 512 Winter 2003

Homework Set #5 – Solutions
1. This problem is essentially Merzbacher, Chapter 18, Problem 4 [or Sakurai, Chapter 5,
Problem 1]. Consider a one-dimensional harmonic oscillator perturbed by a constant
force
H =
p
2
2m
+
1
2

2
x
2
−Fx
a) Show that the first order perturbation in the energy levels vanishes
Since we will need to find the second order perturbation in part b), let us consider
the general matrix element
V
mn
= −F'm
(0)
[x[n
(0)
`
The operator x is given in terms of creation and annihilation operators by x =

¯ h/(2mω)(a

+a). Thus
V
mn
= −F

¯ h
2mω
'm
(0)
[(a

+ a)[n
(0)
`
= −F

¯ h
2mω
[

n + 1 δ
m,n+1
+


j,n−1
]
This indicates that the x operator changes the oscillator number by ±1. In par-
ticular, V
nn
= 0, which demonstrates that the first order energy perturbation
vanishes.
b) Now calculate the eigenenergies E
n
up to second order in the perturbation.
Using the matrix element calculated above, we find
E
(2)
n
=
¸
k=n
[V
kn
[
2
E
(0)
n
−E
(0)
k
=
[V
n+1,n
[
2
E
(0)
n
−E
(0)
n+1
+
[V
n−1,n
[
2
E
(0)
n
−E
(0)
n−1
= F
2
¯ h
2mω
¸
n + 1
−¯ hω
+
n
¯ hω

= −
F
2
2mω
2
Combined with the zeroth order energy, this gives
E
n
= (n +
1
2
)¯ hω −
F
2
2mω
2
c) Show that the second-order perturbation result gives the exact eigenenergies
(which may be obtained by completing the square in H). Explain why this
happens.
1
By completing the square, we find
H =
p
2
2m
+
1
2

2

x −
F

2

2

F
2
2mω
2
=
p
2
2m
+
1
2

2
x
2

F
2
2mω
2
where x = x −F/(mω
2
) is a shifted coordinate. In terms of this new coordinate,
we have an ordinary harmonic oscillator, however with a constant offset in the
potential. We easily read off the eigenenergies as
E
n
= (n +
1
2
)¯ hω −
F
2
2mω
2
(1)
which is identical to the perturbation result of b). Of course, in general we would
apply perturbation theory only when we do not know the exact answer. How-
ever, in this toy example, after completing the square, we see that F enters the
Hamiltonian only quadratically as an overall offset. In particular, we know that
the correct energies, (1), only has F
2
, and no other powers of F in it. Now re-
call that each order in the perturbation theory corresponds to precisely that order
in a series expansion of the small perturbation parameter (which would be F in
this case); first order perturbation gives O(F), second order gives O(F
2
), and so
on. As a result, only the second order perturbation to the energy can contribute
towards the correct answer, and this is in fact what happens.
2. Sakurai, Chapter 5, Problem 2. In nondegenerate time-independent perturbation
theory, what is the probability of finding in a perturbed energy eigenstate [ψ
n
` the
corresponding unperturbed eigenstate [ψ
(0)
n
`? Solve this up to terms of order g
2
.
We recall that the perturbed eigenstate is not necessarily normalized, and may be
written as

n
` = [ψ
(0)
n
` +g[ψ
(1)
n
` +g
2

(2)
n
` +
Since the probability is the amplitude squared, we want to calculate (to second order
in g)
P =


(0)
n

n
`


n

n
`

=
['ψ
(0)
n

n
`[
2

n

n
`
Since all the higher order [ψ
(i>0)
n
` states are orthogonal to [ψ
(0)
n
`, it is easy to see that

(0)
n

n
` = 'ψ
(0)
n

(0)
n
` = 1
and

n

n
` = 'ψ
(0)
n

(0)
n
` + g


(0)
n

(1)
n
` +'ψ
(1)
n

(0)
n
`

+ g
2


(0)
n

(2)
n
` +'ψ
(1)
n

(1)
n
` +'ψ
(2)
n

(0)
n
`

+
= 1 + g
2

(1)
n

(1)
n
` + = 1 + g
2
¸
k=n
[V
kn
[
2
[E
(0)
n
−E
(0)
k
[
2
+
2
Using 1/(1 + x) = 1 −x + , we find
P = 1 −g
2
¸
k=n
[V
kn
[
2
[E
(0)
n
−E
(0)
k
[
2
+
which we verify is less than or equal to one. Clearly, the only possibility of finding
100% probability is if [ψ
n
` is identical to [ψ
(0)
n
`, indicating that the initial eigenstate
remains an eigenstate of the perturbation.
[Yes, this is the same as Wave-function Renormalization on p. 293 of Sakurai!]
3. Consider the 2p levels of hydrogen (m = 0, ±1) subject to a perturbation
V = Ax
2
+ By
2
−(A+B)z
2
a) Write V in terms of components of a rank-2 spherical tensor.
Using the spherical harmonic ‘trick’, we can write out the appropriate rank-2
tensor as
T
(2)
±2
=
1
2
(x ±iy)
2
T
(2)
±1
= ∓(x ±iy)z
T
(2)
0
= −
1

6
(x
2
+ y
2
−2z
2
)
Of course, the actual normalization is arbitrary. I have removed a factor of

15π/8 when compared to the Y
m
l=2
spherical harmonics. In this case, we may
reexpress
x
2
−y
2
= T
(2)
2
+ T
(2)
−2
, x
2
+ y
2
−2z
2
= −

6 T
(2)
0
This allows us to rewrite the perturbation
V =
1
2
(A+ B)(x
2
+y
2
) +
1
2
(A−B)(x
2
−y
2
) −(A+ B)z
2
=
1
2
(A+ B)(x
2
+y
2
−2z
2
) +
1
2
(A−B)(x
2
−y
2
)
= −

3
2
(A+ B)T
(2)
0
+
1
2
(A−B)(T
(2)
2
+ T
(2)
−2
)
(1)
Note that the coefficients of x
2
, y
2
and z
2
had to work out just right for this to
be possible. If instead of (A + B)z
2
, we had something like Cz
2
, then we would
have an added term left over which would be proportional to r
2
= x
2
+ y
2
+ z
2
.
This would correspond to a scalar perturbation in addition to a pure rank-2 tensor
perturbation.
b) Neglecting electron spin, find the “correct” zeroth-order eigenstates and their
corresponding energies. It is sufficient to give the energies in terms of a reduced
matrix element '2p[[T
(2)
[[2p`.
We denote the 2p states as [nlm` = [211`, [210` and [21 −1`. We first observe
that the perturbation will not mix [210` with the other two states [because of the
3
∆m = 0, ±2 selection rule evident from (1)]. So, although all three states are
degenerate, the perturbation is block diagonal in the [210` and ¦[211`, [21 −1`¦
subspaces. This simplification allows us to immediately write down, for the [210`
state
∆E
210
= '210[V [210` = −

3
2
(A+B)'210[T
(2)
0
[210`
= −

3
2
(A+B)'1200[1210`'2p[[T
(2)
[[2p`
=

3
5
(A+ B)'2p[[T
(2)
[[2p`
For the remaining two states, we write out the matrix
V =

'211[V [211` '211[V [21 −1`
'21 −1[V [211` '21 −1[V [21 −1`

= −

3
2
(A+B)

'211[T
(2)
0
[211` 0
0 '21 −1[T
(2)
0
[21 −1`

+
1
2
(A−B)

0 '211[T
(2)
2
[21 −1`
'21 −1[T
(2)
−2
[211` 0

= −

3
2
(A+B)'2p[[T
(2)
[[2p`

'1210[1211` 0
0 '12 −10[121 −1`

+
1
2
(A−B)'2p[[T
(2)
[[2p`

0 '12 −12[1211`
'121 −2[121 −1` 0

=
1
2

3
5
'2p[[T
(2)
[[2p`

−(A+B) (A−B)
(A−B) −(A+B)

Working out the eigenvalues and eigenstates, we find a simple result
∆E
21x
= −

3
5
A'2p[[T
(2)
[[2p` [21x` ≡
1

2

[211` −[21 −1`

∆E
21y
= −

3
5
B'2p[[T
(2)
[[2p` [21y` ≡
1

2

[211` +[21 −1`

Here, the labels x and y were chosen to be suggestive of p
x
and p
y
orbitals. How-
ever, of course, this is just an arbitrary labeling of the eigenstates. To summarize,
the perturbation splits all three 2p states (ignoring spin) to
∆E
210
=

3
5
(A+ B)'2p[[T
(2)
[[2p`, [210`
∆E
21x
= −

3
5
A'2p[[T
(2)
[[2p`, [21x` =
1

2

[211` −[21 −1`

∆E
21y
= −

3
5
B'2p[[T
(2)
[[2p`, [21y` =
1

2

[211` +[21 −1`

Note that the energy shifts are proportional to A, B and −(A + B), the factors
multiplying x
2
, y
2
and z
2
, respectively. The corresponding eigenstates, [21x`,
4
[21y` and [210` are simply the p
x
, p
y
and p
z
orbitals (which are aligned along the
x, y and z axis). So this makes perfect physical sense.
c) Show that the expectation value of L
z
vanishes in each eigenstate found above.
Of course the expectation values of L
z
take on the values 0, ±¯ h in the original
basis states [210` and [21 ±1`. Here, however, we consider
'210[L
z
[210` = 0
'21x[L
z
[21x` =
1
2

'211[ −'21 −1[

L
z

[211` −[21 −1`

=
1
2

'211[L
z
[211` +'21 −1[L
z
[21 −1`

= 0
'21y[L
z
[21y` =
1
2

'211[ +'21 −1[

L
z

[211` +[21 −1`

=
1
2

'211[L
z
[211` +'21 −1[L
z
[21 −1`

= 0
so that the expectation values indeed vanish. It is important to keep in mind that
the expectation values are not the same thing as eigenvalues! The eigenvalues of
L
z
are always 0, ±¯ h for the 2p states.
4. Merzbacher, Chapter 18, Problem 14.
For the Hamiltonian H = A

L
2
+ B¯ h
2
cos 2ϕ with A B, we may take the second
term as a perturbation. Hence
H
0
= A

L
2
= A¯ h
2
( + 1)
for states of angular momentum . For the perturbation, we find it convenient to write
V = B¯ h
2
cos 2ϕ =
1
2
B¯ h
2
(e
2iϕ
+ e
−2iϕ
)
Although the perturbation breaks rotational invariance (after all, it is a hindered rota-
tion), we may nevertheless consider its effect on angular momentum states [m`. In
this case, since Y
m

(θ, ϕ) ∼ e
imϕ
P
m

(cos θ), we see that
'

m

[V [m` =

(Y
m

)

V Y
m

dΩ ∼


0
e
−im

ϕ
(e
2iϕ
+ e
−2iϕ
)e
imϕ
dϕ (rest)
Hence we may deduce that m

and m obey a selection rule ∆m = ±2. This provides
an important simplification, as it indicates that most of the matrix elements of the
perturbation actually vanish. We are now ready to examine the S, P and D levels one
at a time.
For the S level ( = 0)
This state is non-degenerate, and has vanishing zeroth order energy, E
(0)
= 0.
In addition, the first order shift in the energy also vanishes since '00[V [00` = 0
by the ∆m selection rule. We thus have, for the S level
E = 0, [00`
5
Note that, while the energy vanishes up to first order, [00` is not an eigenstate of
H.
For the P levels ( = 1)
At zeroth order, the P levels are three-fold degenerate with E
(0)
= 2A¯ h
2
. For the
first order perturbation, use of the ∆m selection rule indicates that [10` cannot
mix with the other states. Hence it is already the “correct” eigenstate, and does
not get shifted in energy
E = 2A¯ h
2
, [10`
For the remaining [11` and [1 −1` states, we have to diagonalize the perturbation
V =

0 '11[V [1 −1`
'1 −1[V [11` 0

The two non-trivial matrix elements are complex conjugates of each other. So we
only need to compute
'11[V [1 −1` =
1
2
B¯ h
2

(Y
1
1
)

e
2iϕ
Y
−1
1
dϕd cos θ
=
1
2
B¯ h
2


3

sin
2
θ dϕd cos θ = −
1
2
B¯ h
2
Hence
V = −
1
2
B¯ h
2

0 1
1 0

By now, it should be obvious what the eigenvalues and eigenvectors of this matrix
are. Including the zeroth order energy, we have
E = 2A¯ h
2

1
2
B¯ h
2
,
1

2
([11` +[1 −1`)
E = 2A¯ h
2
+
1
2
B¯ h
2
,
1

2
([11` −[1 −1`)
We see that the perturbation completely lifts the degeneracy of the P states.
For the D levels ( = 2)
The D levels are five-fold degenerate at the zeroth order, with E
(0)
= 6A¯ h
2
. In
general, we may have to work out a 5 5 matrix for the perturbation. However,
the ∆m selection rule again helps, and indicates that the five states split up into
two subspaces, one with ¦[21`, [2 −1`¦ and the other with ¦[22`, [20`, [2 −2`¦. For
the former, we have
V =

0 '21[V [2 −1`
'2 −1[V [21` 0

6
where
'21[V [2 −1` =
1
2
B¯ h
2

(Y
1
2
)

e
2iϕ
Y
−1
2
dϕd cos θ
=
1
2
B¯ h
2


15

(sin θ cos θ)
2
dϕd cos θ = −
1
2
B¯ h
2
The eigenenergies and eigenstates in this subspace are hence
E = 6A¯ h
2

1
2
B¯ h
2
,
1

2
([21` +[2 −1`)
E = 6A¯ h
2
+
1
2
B¯ h
2
,
1

2
([21` −[2 −1`)
Finally, turning to the three-dimensional subspace, we have
V =

¸
0 '22[V [20` 0
'20[V [22` 0 '20[V [2 −2`
0 '2 −2[V [20` 0

We evaluate
'22[V [20` =
1
2
B¯ h
2

(Y
2
2
)

e
2iϕ
Y
0
2
dϕd cos θ
=
1
2
B¯ h
2

5
16π

3
2

sin
2
θ(3 cos
2
θ −1)dϕd cos θ = −
1
2

6
B¯ h
2
and note that '20[V [2 −2` gives the same result. Thus
V = −
1
2

6
B¯ h
2

¸
0 1 0
1 0 1
0 1 0

It is easy to check that the matrix of ones and zeros has eigenvalues

2, 0
and −

2, with eigenvectors ( 1

2 1 )
T
, ( 1 0 −1 )
T
and ( 1 −

2 1 )
T
.
Hence the correct eigenenergies and eigenstates are
E = 6A¯ h
2

1
2

3
B¯ h
2
,
1
2
([22` +

2[20` +[2 −2`)
E = 6A¯ h
2
,
1

2
([21` −[2 −2`)
E = 6A¯ h
2
+
1
2

3
B¯ h
2
,
1
2
([22` −

2[20` +[2 −2`)
7
Finally, to summarize, we find, for the S, P and D levels
S : E = 0, [00`
P : E = 2A¯ h
2

1
2
B¯ h
2
,
1

2
([11` +[1 −1`)
E = 2A¯ h
2
, [10`
E = 2A¯ h
2
+
1
2
B¯ h
2
,
1

2
([11` −[1 −1`)
D : E = 6A¯ h
2

1
2
B¯ h
2
,
1

2
([21` +[2 −1`)
E = 6A¯ h
2

1
2

3
B¯ h
2
,
1
2
([22` +

2[20` +[2 −2`)
E = 6A¯ h
2
,
1

2
([21` −[2 −2`)
E = 6A¯ h
2
+
1
2

3
B¯ h
2
,
1
2
([22` −

2[20` +[2 −2`)
E = 6A¯ h
2
+
1
2
B¯ h
2
,
1

2
([21` −[2 −1`)
Note that the P states are split just as they were in problem 3).
8

In particular. we find H= F 1 p2 + mω 2 x − 2m 2 mω 2 1 p2 F2 + mω 2 x2 − = 2m 2 2mω 2 2 − F2 2mω 2 where x = x − F/(mω 2 ) is a shifted coordinate. We easily read off the eigenenergies as En = (n + 1 )¯ ω − 2 h F2 2mω 2 (1) which is identical to the perturbation result of b). first order perturbation gives O(F ). and so on. it is easy to see that (0) (0) (0) (0) ψn |ψn = ψn |ψn = 1 and (0) (0) ψn |ψn = ψn |ψn + g (0) (1) (1) (0) ψn |ψn + ψn |ψn + g2 (0) (2) (1) (1) (2) (0) ψn |ψn + ψn |ψn + ψn |ψn +··· (0) (1) (1) = 1 + g 2 ψn |ψn + · · · = 1 + g 2 k=n |Vkn |2 |En − Ek |2 (0) +··· 2 . Problem 2. However. and this is in fact what happens. We recall that the perturbed eigenstate is not necessarily normalized. in general we would apply perturbation theory only when we do not know the exact answer.By completing the square. what is the probability of finding in a perturbed energy eigenstate |ψn the (0) corresponding unperturbed eigenstate |ψn ? Solve this up to terms of order g 2 . we see that F enters the Hamiltonian only quadratically as an overall offset. and no other powers of F in it. Of course. after completing the square. In nondegenerate time-independent perturbation theory. Sakurai. we want to calculate (to second order in g) (0) (0) | ψn |ψn |2 ψn |ψn = P = ψn |ψn ψn |ψn Since all the higher order |ψn (i>0) states are orthogonal to |ψn . second order gives O(F 2 ). In terms of this new coordinate. Chapter 5. As a result. 2. only has F 2 . (1). we have an ordinary harmonic oscillator. we know that the correct energies. in this toy example. only the second order perturbation to the energy can contribute towards the correct answer. Now recall that each order in the perturbation theory corresponds to precisely that order in a series expansion of the small perturbation parameter (which would be F in this case). however with a constant offset in the potential. and may be written as (0) (1) (2) |ψn = |ψn + g|ψn + g 2 |ψn + · · · Since the probability is the amplitude squared.

[Yes. this is the same as Wave-function Renormalization on p. We first observe that the perturbation will not mix |210 with the other two states [because of the 3 . I have removed a factor of m 15π/8 when compared to the Yl=2 spherical harmonics. Using the spherical harmonic ‘trick’. In this case. If instead of (A + B)z 2 . This allows us to rewrite the perturbation V = 1 (A + B)(x2 + y 2 ) + 1 (A − B)(x2 − y 2 ) − (A + B)z 2 2 2 = 1 (A + B)(x2 + y 2 − 2z 2 ) + 1 (A − B)(x2 − y 2 ) 2 2 3 2 (A (1) =− + (2) B)T0 + 1 (A − 2 (2) B)(T2 + (2) T−2 ) Note that the coefficients of x2 . It is sufficient to give the energies in terms of a reduced matrix element 2p||T (2) ||2p . This would correspond to a scalar perturbation in addition to a pure rank-2 tensor perturbation. y 2 and z 2 had to work out just right for this to be possible. ±1) subject to a perturbation V = Ax2 + By 2 − (A + B)z 2 a) Write V in terms of components of a rank-2 spherical tensor.Using 1/(1 + x) = 1 − x + · · ·. we may reexpress √ (2) (2) (2) x2 + y 2 − 2z 2 = − 6 T0 x2 − y 2 = T2 + T−2 . b) Neglecting electron spin. we had something like Cz 2 . we can write out the appropriate rank-2 tensor as (2) T±2 = 1 (x ± iy)2 2 T±1 = ∓(x ± iy)z T0 (2) 1 = − √6 (x2 + y 2 − 2z 2 ) (2) Of course. |210 and |21 −1 . Consider the 2p levels of hydrogen (m = 0. find the “correct” zeroth-order eigenstates and their corresponding energies. then we would have an added term left over which would be proportional to r 2 = x2 + y 2 + z 2 . the only possibility of finding (0) 100% probability is if |ψ n is identical to |ψn . we find P = 1 − g2 |Vkn |2 2 k=n |En − Ek | (0) (0) +··· which we verify is less than or equal to one. the actual normalization is arbitrary. We denote the 2p states as |nlm = |211 . 293 of Sakurai!] 3. Clearly. indicating that the initial eigenstate remains an eigenstate of the perturbation.

the labels x and y were chosen to be suggestive of p x and py orbitals. So. 3 5A 3 5B |210 |21x = |21y = 1 √ 2 1 √ 2 − − 2p||T (2) ||2p . we write out the matrix V= =− 211|V |211 21 −1|V |211 3 2 (A 211|V |21 −1 21 −1|V |21 −1 211|T0 |211 0 (2) + B) 0 21 −1|T0 |21 −1 211|T2 |21 −1 0 1210|1211 0 0 12 −10|121 −1 12 −12|1211 0 (2) (2) + 1 (A − B) 2 =− 3 (A 2 0 (2) 21 −1|T−2 |211 + B) 2p||T (2) ||2p + 1 (A − B) 2p||T (2) ||2p 2 = 1 2 3 5 0 121 −2|121 −1 (A − B) −(A + B) 2p||T (2) ||2p −(A + B) (A − B) Working out the eigenvalues and eigenstates. respectively. B and −(A + B). |21x . although all three states are degenerate. The corresponding eigenstates.∆m = 0. we find a simple result ∆E21x = − ∆E21y = − 3 5A 3 5B 2p||T (2) ||2p 2p||T (2) ||2p |21x ≡ |21y ≡ 1 √ 2 1 √ 2 |211 − |21 −1 |211 + |21 −1 Here. 4 . for the |210 state ∆E210 = 210|V |210 = − =− = 3 2 (A 3 2 (A 3 5 (A + B) 210|T0 |210 + B) 1200|1210 2p||T (2)||2p (2) + B) 2p||T (2) ||2p For the remaining two states. the perturbation splits all three 2p states (ignoring spin) to ∆E210 = ∆E21x = ∆E21y = 3 (A 5 + B) 2p||T (2) ||2p . ±2 selection rule evident from (1)]. To summarize. the factors multiplying x2 . y 2 and z 2 . the perturbation is block diagonal in the |210 and {|211 . |211 − |21 −1 |211 + |21 −1 Note that the energy shifts are proportional to A. However. of course. 2p||T (2) ||2p . This simplification allows us to immediately write down. |21 − 1 } subspaces. this is just an arbitrary labeling of the eigenstates.

Merzbacher. we may take the second ) VY ∗ m dΩ ∼ 2π 0 e−im ϕ (e2iϕ + e−2iϕ )eimϕ dϕ × (rest) Hence we may deduce that m and m obey a selection rule ∆m = ±2. Problem 14. it is a hindered rotation). In this case. we consider 210|Lz |210 = 0 21x|Lz |21x = = 21y|Lz |21y = = 1 2 1 2 1 2 1 2 211| − 21 −1| Lz |211 − |21 −1 211|Lz |211 + 21 −1|Lz |21 −1 211| + 21 −1| Lz |211 + |21 −1 211|Lz |211 + 21 −1|Lz |21 −1 =0 =0 so that the expectation values indeed vanish. we find it convenient to write V = B¯ 2 cos 2ϕ = 1 B¯ 2 (e2iϕ + e−2iϕ ) h 2 h Although the perturbation breaks rotational invariance (after all. For the perturbation.|21y and |210 are simply the px . for the S level E = 0. In addition. ±¯ for the 2p states. c) Show that the expectation value of Lz vanishes in each eigenstate found above. P and D levels one at a time. E (0) = 0. as it indicates that most of the matrix elements of the perturbation actually vanish. ±¯ in the original h basis states |210 and |21 ±1 . y and z axis). ϕ) ∼ eimϕ P m (cos θ). It is important to keep in mind that the expectation values are not the same thing as eigenvalues! The eigenvalues of h Lz are always 0. and has vanishing zeroth order energy. 5 |00 . We are now ready to examine the S. For the S level ( = 0) This state is non-degenerate. Chapter 18. we may nevertheless consider its effect on angular momentum states | m . h For the Hamiltonian H = AL 2 + B¯ 2 cos 2ϕ with A term as a perturbation. So this makes perfect physical sense. py and pz orbitals (which are aligned along the x. 4. Here. Of course the expectation values of Lz take on the values 0. since Y m (θ. the first order shift in the energy also vanishes since 00|V |00 = 0 by the ∆m selection rule. This provides an important simplification. however. we see that m |V | m = (Y m B. We thus have. Hence h H0 = AL 2 = A¯ 2 ( + 1) for states of angular momentum .

Note that. h 2 1 √ (|11 2 1 √ (|11 2 + |1 −1 ) − |1 −1 ) We see that the perturbation completely lifts the degeneracy of the P states. and indicates that the five states split up into two subspaces. |00 is not an eigenstate of H. For the former. In general. However. while the energy vanishes up to first order. the ∆m selection rule again helps. Hence it is already the “correct” eigenstate. For the first order perturbation. h For the remaining |11 and |1 −1 states. and does not get shifted in energy |10 E = 2A¯ 2 . For the D levels ( = 2) h The D levels are five-fold degenerate at the zeroth order. So we only need to compute 11|V |1 −1 = 1 B¯ 2 2 h (Y11 )∗ e2iϕ Y1−1 dϕ d cos θ 3 8π sin2 θ dϕ d cos θ = − 1 B¯ 2 2 h = 1 B¯ 2 − 2 h Hence h V = − 1 B¯ 2 2 0 1 1 0 By now. one with {|21 . we have V= 0 2 −1|V |21 6 21|V |2 −1 0 . with E (0) = 6A¯ 2 . Including the zeroth order energy. For the P levels ( = 1) h At zeroth order. the P levels are three-fold degenerate with E (0) = 2A¯ 2 . |2 −2 }. |2 −1 } and the other with {|22 . use of the ∆m selection rule indicates that |10 cannot mix with the other states. |20 . it should be obvious what the eigenvalues and eigenvectors of this matrix are. we may have to work out a 5 × 5 matrix for the perturbation. h 2 h h E = 2A¯ 2 + 1 B¯ 2 . we have E = 2A¯ 2 − 1 B¯ 2 . we have to diagonalize the perturbation V= 0 1 −1|V |11 11|V |1 −1 0 The two non-trivial matrix elements are complex conjugates of each other.

( 1 0 −1 ) and ( 1 − 2 and − 2. 0 T 1) .where 21|V |2 −1 = 1 B¯ 2 2 h (Y21 )∗ e2iϕ Y2−1 dϕ d cos θ 15 8π (sin θ cos θ)2 dϕ d cos θ = − 1 B¯ 2 2 h = 1 B¯ 2 − 2 h The eigenenergies and eigenstates in this subspace are hence E = 6A¯ 2 − 1 B¯ 2 . turning to the three-dimensional subspace. h 2 3 1 2 (|22 1 √ (|21 2 1 2 (|22 + √ 2|20 + |2 −2 ) − |2 −2 ) √ − 2|20 + |2 −2 ) 7 . we have 0 V =  20|V |22 0 We evaluate 22|V |20 = 1 B¯ 2 h 2 = 1 B¯ 2 h 2 (Y22 )∗ e2iϕ Y20 dϕ d cos θ 5 16π 3 2 1 sin2 θ(3 cos2 θ − 1)dϕ d cos θ = − 2√6 B¯ 2 h  22|V |20 0 2 −2|V |20  0 20|V |2 −2  0 and note that 20|V |2 −2 gives the same result. h 2 3 1 √ B¯ 2 . It is easy to check that the matrix of ones and zeros has eigenvalues √ √ √ T T 2 1 ) . h 2 h E = 6A¯ 2 + 1 B¯ 2 . with eigenvectors ( 1 Hence the correct eigenenergies and eigenstates are E = 6A¯ 2 − h E = 6A¯ 2 . Thus 0 1 h V = − √ B¯ 2  1 2 6 0  1 0 1  0 1 0 √ 2. h 2 h 1 √ (|21 2 1 √ (|21 2 + |2 −1 ) − |2 −1 ) Finally. h E = 6A¯ 2 + h 1 √ B¯ 2 .

h 2 E = 6A¯ 2 − h E = 6A¯ 2 . h 2 1 √ B¯ 2 . h 2 3 1 B¯ 2 . we find. for the S.Finally. P and D levels S: P : E = 0. h E = 2A¯ + 1 B¯ . h h 2 E = 2A¯ 2 . h 2 3 2 2 |00 1 √ (|11 2 + |1 −1 ) − |1 −1 ) |10 1 √ (|11 2 1 √ (|21 2 + |2 −1 ) √ 1 (|22 + 2|20 + |2 −2 ) 2 − |2 −2 ) √ − 2|20 + |2 −2 ) − |2 −1 ) 1 √ (|21 2 1 2 (|22 1 √ (|21 2 Note that the P states are split just as they were in problem 3). h 2 h D: h E = 6A¯ 2 − 1 B¯ 2 . 8 . to summarize. h E = 6A¯ 2 + h E = 6A¯ 2 + h 1 √ B¯ 2 . E = 2A¯ 2 − 1 B¯ 2 .