Chemistry 532

Problem Set 8
Fall, 2012
Solutions
1. Evaluate the commutators [L̂i , x2 + y 2 + z 2 ] where i = x, y or z. [Hint: This problem
can be done in two lines if you think.]
Answer:
[L̂i , x2 + y 2 + z 2 ] = [L̂i , r2 ] = 0
because L̂i is independent of r for all i.

2. Let ψ be an eigenfunction of L̂z . Show that

< ψ|L̂x |ψ >=< ψ|L̂y |ψ >= 0.

Answer: Let
L̂z ψ = mh̄ψ
We have
1
L̂x = [L̂y , L̂z ]
ih̄
Then
1
hψ|L̂x |ψi = hψ|[L̂y , L̂z ]|ψi
ih̄
1
= hψ|L̂y L̂z − L̂z L̂y |ψi
ih̄
mh̄
= hψ|L̂y − L̂y |ψi = 0
ih̄
We also have
1
L̂y = [L̂z , L̂x ]
ih̄
Then
1
hψ|L̂y |ψi = hψ|[L̂z , L̂x ]|ψi
ih̄
1
= hψ|L̂z L̂x − L̂x L̂z |ψi
ih̄
mh̄
= hψ|L̂x − L̂x |ψi = 0
ih̄

1
3. Show that if any operator, Â commutes with two components of the angular momen-
tum, it commutes with the third.
Answer: Let [Â, L̂x ] = [Â, L̂y ] = 0. We must show that [Â, L̂z ] = 0 as well. Now

1
[Â, L̂z ] = [Â, [L̂z , L̂y ]]
ih̄
1
= {ÂL̂x L̂y − ÂL̂y L̂x − L̂x L̂y  + L̂y L̂x Â}
ih̄
1
= {ÂL̂x L̂y − ÂL̂y L̂x − ÂL̂x L̂y + ÂL̂y L̂x } = 0
ih̄
The same proof holds for the other components of L. ~

4. Show that the spherical harmonics are eigenfunctions of the operator L̂2x + L̂2y , and
determine the eigenvalues. This problem should take about 4 lines of math.
Answer:
L̂2 = L̂2x + L̂2y + L̂2z
L̂2x + L̂2y = L̂2 − L̂2z
(L̂2x + L̂2y )Y`m = (L̂2 − L̂2z )Y`m
= h̄2 [`(` + 1) − m2 ]Y`m
The eigenvalues are h̄2 [`(` + 1) − m2 ].

5. Calculate the first two non-vanishing terms in the expansion of the function
(
−1 −1 ≤ x ≤ 0
F (x) =
+1 0<x≤1

in Legendre polynomials. [See Table 6-3 on page 283 of the text.]

Answer: ∞ X
F (x) = A`0 P`0 (x)
`0 =0
Z 1 ∞
X Z 1
F (x)P` (x) dx = A` 0 P`0 (x)P` (x) dx
−1 `0 =0 −1

∞
X 2
= A` 0 δ`,`0
`0 =0
2`0 +1
2
= A`
2` + 1
2` + 1 Z 1
A` = F (x)P` (x) dx
2 −1

2
 1Z 1 1 Z0 Z 1
A0 = F (x) dx = [− dx + dx] = 0
2 −1 2 −1 0

3Z 1 Z 1
3
A1 = x dx = 3 x dx =
2 −1 0 2
Z 1
51
A2 = (3x2 − 1)F (x) dx = 0
2 2 −1
7Z 1 3 5 3
 
A3 = x − x F (x) dx
2 −1 2 3
Z 1 
3 5 3

=7 x − x dx
0 2 3
21 5 1 7
 
= − =−
2 12 2 8
Then
3 7
F (x) = P1 (x) − P3 (x) + . . .
2 8
6. Schmidt orthogonalize the set of functions {1, x, x2 , x3 , . . .} on the interval −1 ≤ x ≤ 1,
and show that the first three members of the orthogonal set at proportional to the first
three Legendre polynomials.
Answer:
v1 = 1 P0 (x) = 1
v2 = x + av1
Z 1 Z 1
hv1 |v2 i = x dx + a dx = 0
−1 −1

0 + 2a = 0 a=0
v2 = x P1 (x) = x
v3 = x2 + bx + c = x2 + bv2 + cv1
Z 1 Z 1
2
hv1 |v3 i = x dx + c dx = 0
−1 −1

1Z 1 2 12 1
c=− x dx = − =−
2 −1 23 3
Z 1 Z 1
hv2 |v3 i = x3 dx + b x2 dx = 0
−1 −1

2
0+ b=0 b=0
3
Then
1 1 3 2 1 3
 
2
v3 = x − P2 (x) = (3x2 − 1) = x − = v3
3 2 2 3 2

3
7. Determine uncertainty relations between the three components of the linear momentum
and the three components of the angular momentum of a system.
Answer:
1
∆px ∆Lx ≥ |h[p̂x , L̂x ]i|
2
" #
2 ∂ ∂ ∂
[p̂x , L̂x ] = −h̄ ,y −z =0
∂x ∂z ∂y
Then
∆px ∆Lx = 0
1
∆px ∆Ly ≥ |h[p̂x , L̂y ]i|
2
" #
2 ∂ ∂ ∂
[p̂x , L̂y ] = −h̄ ,z −x
∂x ∂x ∂z
!
2 ∂ ∂ ∂ ∂
= h̄ x −x
∂x ∂z ∂z ∂x
∂
= h̄2 = ih̄p̂z
∂z
Then
h̄
∆px ∆Ly ≥ |hpz i|
2
Next, !
2 ∂ ∂ ∂
[p̂x , L̂z ] = −h̄ ,x −y
∂x ∂y ∂x
∂
= −h̄2 = −ih̄p̂y
∂y
so that
h̄
∆px ∆Lz ≥ |hpy i|
2
In a similar way
h̄ h̄
∆py ∆Lx ≥ |hpz i| ∆py ∆Ly = 0 ∆py ∆Lz ≥ |hpx i|
2 2
and
h̄ h̄
∆pz ∆Lx ≥ |hpy i| ∆pz ∆Ly ≥ |hpx i| ∆pz ∆Lz = 0
2 2
8. A particle of mass m is confined to move on the surface of a sphere of radius R. The
state of the particle at time t = 0 is described by the wavefunction
 1/2
1
Ψ(θ, φ) = [Y11 (θ, φ) + Y10 (θ, φ) + Y1−1 (θ, φ)]
3
where Ylm (θ, φ) are the spherical harmonics.

4
 (a) If Lz is measured for this system at time t = 0, what are the possible outcomes
of the measurement and with what relative probabilities?
Answer:
Lz = −h̄, 0, h̄
each with probability !2
1 1
P = √ =
3 3
(b) If L2 is measured for this system at time t = 0, what are the possible outcomes
of the measurement and with what relative probabilities?
Answer:
L2 = h̄2 1(1 + 1) = 2h̄2 P =1
(c) What is the average value of Lx over Ψ(θ, φ)?
Answer:
L̂+ = L̂x + iL̂y L̂− = L̂x − iL̂y
so that
1
L̂x = (L̂+ + L̂− )
2
1 1
 
hψ|L̂x |ψi = Y11 + Y10 + Y1−1 (L̂+ + L̂− ) Y11 + Y10 + Y1−1
3 2
h̄ √ √ √ √
= hY11 + Y10 + Y1−1 |( 2|Y11 i + 2|Y10 i + 2|Y10 i + 2|Y1−1 i)
6
√
h̄ √ 2 2h̄
= 4 2=
6 3
9. The quantum mechanical Hamiltonian operator for a two-dimensional particle of mass
m confined to move on the perimeter of a ring of radius R is given by

h̄2 d2
Ĥ = −
2mR2 dφ2
√
(a) Show that the set of functions {1/ 2π exp(inφ)} form a normalized complete set
of simultaneous eigenfunctions of the Hamiltonian and the z-component of the
angular momentum. Impose boundary conditions on the set of wavefunctions to
determine the possible values of the quantum number n.
Answer:
h̄ d inφ
L̂z einφ = e = nh̄einφ
i dφ
inφ h̄2 d2 inφ n2 h̄2 inφ
Ĥe =− e = e
2mR2 dφ2 2mR2
einφ = ein(φ+2π) = einφ ein2π

5
 Then
ein2π = 1 n = 0, ±1, ±2, . . .
Z 2π
1 2π
e−inφ einφ dφ = =1
2π 0 2π
(b) Suppose at time t = 0 the quantum state of the particle is described by the wave-
function ψ(φ) = N cos2 (φ) where N is the normalization. If the z-component of
the angular momentum and the energy of the particle are measured simultane-
ously at time t = 0, what values can be obtained for each observable and with
what probabilities?
Answer:
Z 2π 2π
2 4 2 3φ 6π
N cos φ dφ = N = N2 =1
0 8 0 8
1/2
4

N=
3π
1/2 ∞
4 1

cos2 φ = cn √ einφ
X
3π n=−∞ 2π
 1/2
4 1 Z 2π
cn = cos2 φe−inφ dφ
6 π 0
 1/2
4 1 Z 2π 1 iφ
= (e + e−iφ )2 e−inφ dφ
6 π 0 4
 1/2 
2 11

= δn,2 + δn,−2 + δn,0
3 2 2
Then for Lz we can measure 2h̄ or −2h̄ with probabilities of 1/6 each or we can
find Lz = 0 with probability 2/3. The energy levels are

n2 h̄2
En =
2mR2
We can obtain from an energy measurement

4h̄2
E= i.e. n = 2
2mR2
with probability 1/3 and E = 0 with probability 2/3.

10. For the 1s ground state of the hydrogen atom, find

(a) hri
Answer: !1/2
1
ψ1s (r) = e−r/a0
πa30

6
 1 Z ∞ Z π Z 2π
hri = 3 dr dθ dφ r2 sin θe−r/a0 re−r/a0
πa0 0 0 0

4π Z ∞
= dr r3 e−2r/a0
πa0 0
6a40
! !
4 3
= = a0
a30 24 2
(b) h1/ri
Answer: !
1 4 Z∞
 
= dr r e−2r/a0
r a30 0
a20
! !
4 1
= =
a30 4 a0
(c) h1/r2 i
Answer: !
1 4 Z∞
 
= dr e−2r/a0
r2 a30 0
!
4 a0 2

= =
a30 2 a20
(d) hT i
Answer:
h̄2 2 h̄2 ∂ 2 ∂ L̂2
− ∇ =− r +
2µ 2µr2 ∂r ∂r 2µr2
L̂2 ψ1s (r) = 0
1 d 2d d2 2 d
2
r = 2
+
r dr dr dr r dr
Then
d2
!
2 d
T̂ ψ1s (r) = 2
+ ψ1s (r)
dr r dr
Now
d −r/a0 1
e = − e−r/a0
dr a0
and
d2 −r/a0 1
2
e = 2 e−r/a0
dr a0
Then
h̄2 2 −r/a0 h̄2
!
1 2
− ∇e =− 2
− e−r/a0
2µ 2µ a0 ra0

7
 and
h̄2 h̄2 1
 
hT i = − hψ1s |ψ1s i +
2µa20 2µa0 r
2 2
h̄ h̄ h̄2
=− + =
2µa20 µa20 2µa20
11. An electron in a hydrogen atom occupies a 3dxy orbital. If Lz , the z-component of the
angular momentum of the electron is measured, determine what values can be obtained
and with what probabilities?
Answer: !1/2
1 1
Ψ3dxy (r, θ, φ) = √ 7
r2 e−r/3a0 sin2 θ sin 2φ
81 2π a0
Because
h̄ ∂
L̂z =
i ∂φ
we need only focus on the φ part of the wavefunction; i.e. we take
ψ(φ) = A sin 2φ
Normalizing ψ we have
Z 2π 4π
1 Z 4π 1 y 1

A2 dφ sin2 2φ = A2 dy sin2 y = A2 − sin 2y
0 2 0 2 2 4 0
2
=A π=1
or
1
ψ(φ) = √ sin 2φ
π
√
The normalized eigenfunctions of L̂z are {1/ 2πeinφ }, n = 0, ±1, ±2, . . .. Then
∞
1 1
cn √ einφ
X
√ sin 2φ =
π n=−∞ 2π
or
1 Z 2π −inφ
cn = √ e sin 2φ dφ
π 2 0
1 Z 2π −inφ 1 i2φ
= √ e [e − e−i2φ ] dφ
π 2 0 2i
1 Z 2π iφ(2−n)
= √ [e − e−iφ(2+n) ] dφ
2iπ 2 0
2π
= √ [δn,2 − δn,−2 ]
2πi 2
1
= √ [δn,2 − δn,−2 ]
i 2
Then a measurement of Lz can find Lz = ±2h̄ each with a probability of 1/2.