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You are on page 1of 8

**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

mω

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

+

√

nδ

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

mω

2

x −

F

mω

2

2

−

F

2

2mω

2

=

p

2

2m

+

1

2

mω

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

[ψ

n

` = [ψ

(0)

n

` +g[ψ

(1)

n

` +g

2

[ψ

(2)

n

` +

Since the probability is the amplitude squared, we want to calculate (to second order

in g)

P =

'ψ

(0)

n

[ψ

n

`

'ψ

n

[ψ

n

`

=

['ψ

(0)

n

[ψ

n

`[

2

'ψ

n

[ψ

n

`

Since all the higher order [ψ

(i>0)

n

` states are orthogonal to [ψ

(0)

n

`, it is easy to see that

'ψ

(0)

n

[ψ

n

` = 'ψ

(0)

n

[ψ

(0)

n

` = 1

and

'ψ

n

[ψ

n

` = 'ψ

(0)

n

[ψ

(0)

n

` + g

'ψ

(0)

n

[ψ

(1)

n

` +'ψ

(1)

n

[ψ

(0)

n

`

+ g

2

'ψ

(0)

n

[ψ

(2)

n

` +'ψ

(1)

n

[ψ

(1)

n

` +'ψ

(2)

n

[ψ

(0)

n

`

+

= 1 + g

2

'ψ

(1)

n

[ψ

(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 ∼

2π

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

8π

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

8π

(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 .

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