Chemistry 432

Problem Set 4
Spring 2018
Solutions

1.
6 6

V0

I II III

0 a b c

A one-dimensional particle of mass m is confined to move under the influence of the

potential
0≤x≤a


 0
 V a<x≤b

V (x) =  0
 0
 b≤x≤c
∞ elsewhere


and pictured above. Give the Schrödinger equation for the particle in regions I, II and
III, and impose the proper boundary conditions for the wavefunctions in each of the
three regions.
Answer:
h̄2 d2 ψI
− = EψI
2m dx2
h̄2 d2 ψII
− + V0 ψII = EψII
2m dx2
1
 h̄2 d2 ψIII
− = EψIII
2m dx2
ψI (0) = 0
ψI (a) = ψII (a) ψI0 (a) = ψII
0
(a)
0 0
ψII (b) = ψIII (b) ψII (b) = ψIII (b)
ψIII (c) = 0

2.

V0

I II III

0 a b

A particle of mass m moves under the influence of the potential function pictured
above and defined by 
 0
 0≤x≤a
V (x) =  V0 a < x ≤ b

0 x>b
Give the Schrödinger equation for the particle in the three regions I (0 ≤ x ≤ a), II (a <
x ≤ b) and III(x > b) depicted in the figure, defining ψI (x) to be the wavefunction for
region I, ψII (x) to be the wavefunction for region II and ψIII (x) to be the wavefunction
for region III. Give the appropriate boundary conditions for ψI (x), ψII (x) and ψIII (x).
Answer:
h̄2 d2 ψI
− = EψI
2m dx2
h̄2 d2 ψII
− + V0 ψII = EψII
2m dx2
h̄2 d2 ψIII
− = EψIII
2m dx2

2
 ψI (0) = 0
ψI (a) = ψII (a) 0
ψI0 (a) = ψII (a)
0 0
ψII (b) = ψIII (b) ψII (b) = ψIII (b)

3. Show that the wavefunction

2 /2
ψ(x) = e−αx
with α = µω/h̄ satisfies the one-dimensional Schrödinger equation for a harmonic
oscillator of reduced mass µ and angular frequency ω. Be sure to identify the energy
associated with ψ(x).
Answer
h̄2 d2 ψ 1 2 2
Ĥψ = − + µω x ψ = Eψ
2µ dx2 2
2 /2 2 /2
ψ 0 (x) = −αxe−αx ψ 00 (x) = [−α + α2 x2 ]e−αx
h̄2 2 1 2
Ĥψ = − [−α + α2 x2 ]e−αx /2 + µω 2 x2 e−αx /2
2µ 2
" 2
h̄2 µ2 ω 2 1 2
!#
h̄ µω 2 /2
= − x2 − + µω e−αx
2µ h̄ 2µ h̄2 2
h̄ω −αx2 /2
= e
2
so that
h̄ω
E=
2
4. Show that the wavefunction

ψ(x) = x exp(−mωx2 /2h̄)

is an eigenfunction of the Hamiltonian operator for a harmonic oscillator of mass m

and natural frequency ω. What energy is associated with this wavefunction?
Answer:
h̄2 d2 1
Ĥ = − 2
+ mω 2 x2
2m dx 2
2 /2h̄
ψ = xe−mωx
dψ mω 2
 
2
= e−mωx /2h̄ 1 − x
dx h̄
d2 ψ
" #
mω 2mω mω 2 3
 
−mωx2 /2h̄
=e − x− x+ x
dx2 h̄ h̄ h̄
Then
h̄2 d2 ψ 1 3 1 1 3
 
2 2
− 2
+ mω 2 x2 ψ = e−mωx /2h̄ h̄ωx − mω 2 x3 + mω 2 x3 = h̄ωxe−mωx /2h̄
2m dx 2 2 2 2 2

3
 3
= h̄ωψ(x)
2
Then
3
E = h̄ω
2
5. Consider the wavefunction given in problem 4.

(a) Normalize the wavefunction.

Answer Z ∞ 2 /h̄
N 2
x2 e−mωx dx = 1
−∞
√ !3/2
π h̄
= N2
2 mω
Then " 3/2 #1/2
2 mω

N= √
π h̄
(b) Calculate the expectation value of the kinetic energy of the oscillator using this
wavefunction.
Answer:
h̄2 d2
3/2 Z ∞ !
2 mω

−mωx2 /2h̄ 2
hKi = √ xe − 2
xe−mωx /2h̄ dx
π h̄ −∞ 2m dx
Using the expression for the second derivative from problem 4
h̄2 2
3/2 Z ∞ " 2 #
mω mω 2mω mω
 
−mωx2 /2h̄ 2 /2h̄
hKi = − √ xe − x− x+ x 3
e−mωx dx
2m π h̄ −∞ h̄ h̄ h̄

h̄2
3/2 Z ∞ " #
mω 3mω 2 mω 2 4
  
−mωx2 /h̄
= √ e x − x dx
m π h̄ −∞ h̄ h̄
 √ !3/2  √ !5/2 
h̄2
3/2
mω 3mω π h̄ mω 2 3 π h̄
 
= √  − 
m π h̄ h̄ 2 mω h̄ 4 mω
3
= h̄ω
4
(c) As what point(s) in space is the oscillator most likely to be found?
Answer:
d 2 −mωx2 /h̄
xe
dx
3 mω
 
−mωx2 /h̄
=e 2x − 2x =0
h̄
mω 3
2x − 2 x =0
h̄
4
 s
h̄
x=±
mω
(d) What characteristics of the wavefunction of problem 4 indicate that the energy
associated with the wavefunction is not the ground state energy?
Answer:
The wavefunction has a node, so that the wavefunction cannot represent the
ground state.
6. Explicitly calculate hV i and hKi for the ground state of a harmonic oscillator of mass
m and frequency ω, and show that hKi = hV i.
Answer:
µω
α=
h̄
 1/4
α 2
ψ0 (x) = e−αx /2
π
Z ∞  1/4  1/4
α 2 1 α 2
hV i = e−αx /2 µω 2 x2 e−αx /2 dx
−∞ π 2 π
 1/2 Z ∞
α 1 2 2
= µω x2 e−αx dx
π 2 −∞
√
µω 2 µω 2 h̄
 1/2
α 1 2 π h̄ω
= µω 3/2
= = =
π 2 2α 4α 4µω 4
h̄2 α d2 −αx2 /2
 1/2 Z ∞
2 /2
hKi = − e−αx e dx
2µ π −∞ dx2
2  1/2 Z ∞
h̄ α 2 /2 d 2
=− e−αx [−αxe−αx /2 ]dx
2µ π −∞ dx
h̄2 α 1/2 Z ∞
 
2 /2 2 /2
=− e−αx [−α + α2 x2 ]e−αx dx
2µ π −∞

h̄2 α
 1/2  Z ∞ Z ∞ 
2 2
=− −α e−αx dx + α2 e−αx x2 dx
2µ π −∞ −∞
" 2 2
# 2
h̄ h̄ h̄ µω h̄ω
= α− α = =
2µ 4µ 4µ h̄ 4
Then
hKi = hV i
7. A quantum particle of mass m is subjected to the potential energy function
(
∞ x<0
V (x) = 1 2 2
2
mω x x >0
where ω is a constant having units of frequency. Note that the domain of this system
can be taken to be 0 < x < ∞ .

5
(a) Give the boundary conditions that are appropriate for the wavefunctions which
are solutions to the time-independent Schrödinger equation for the particle.
Answer:
lim ψ(x) = 0
x→∞

lim ψ(x) = 0
x→0

(b) Show that the non-normalized wavefunction

ψ(x) = N x exp(−x2 /2α2 )

where !1/2
h̄
α=
mω
satisfies the boundary conditions specified in part “a”.
Answer:
For
2 2
ψ(x) = N xe−x /2α
ψ(0) = 0 and
lim ψ(x) = 0
x→∞

(c) Normalize the wavefunction given in part “b”.

Answer: Z ∞ √
2 2 −x2 /α2 2 π 3
N xe dx = N α =1
0 4
!1/2
4
N= √ 3
πα
!1/2
4 2 /2α2
ψ(x) = √ 3 xe−x
πα
(d) Determine the value of x at which the particle in the quantum state defined in
part “b” of this problem is most likely to be found.
Answer:
2x3
" #
d 2 −x2 /α2 −x2 /α2
xe =e 2x − 2 = 0
dx α
at
x=α
(e) Calculate the expectation value of the momentum p for the particle in the quan-
tum state defined in part “b” of this problem.
Answer:
4 h̄ Z ∞ −x2 /2α2 d −x2 /2α2
hpi = √ 3 xe xe dx
πα i 0 dx

6
 x2
" !#
4h̄ Z ∞ −x2 /2α2 −x2 /2α2
= √ 3 xe e 1− 2
i πα 0 α
α2 1 α4
" #
4h̄
= √ 3 − 2 =0
i πα 2 α 2
8. In problem 7 we have considered the “half oscillator” of mass m and natural frequency
2
ω, and we verified that ψ1 (x) = N xe−αx /2 with α = mω/h̄ and N the normalization
factor, is the ground-state eigenfunction of the Hamiltonian operator for 0 ≤ x < ∞.
Determine an expression for the ratio hxi/xmp where hxi is the expectation value of
x for the half oscillator in its ground state and xmp is the most likely location for the
half oscillator in its ground state.
Answer √
2
Z ∞
2 −αx2 2 π 2α3/4
N xe dx = N =1 N = 1/4
0 4α3/2 π
Z ∞
4α3/2 3 −αx2 4α3/2 1 2
 
hxi = x e dx = =√
0 π 1/2 π 1/2 2α2 πα
d 2 −αx2 2
xe = (2x − 2αx3 )e−αx = 0 at
dx
1
xmp = √
α
Then
hxi 2
=√
xmp π

9. The normalized wavefunction for the first excited state of a harmonic oscillator of
mass m and natural frequency ω having potential energy V (x) = 1/2 mω 2 x2 and total
energy E1 = 3h̄ω/2 is given by
!1/4
4α3 2 /2
ψ1 (x) = xe−αx
π

where α = mω/h̄. Show that the probability that an oscillator in its first excited state
is found in the tunneling region is given by
4 Z∞ 2
P = √ √ y 2 e−y dy
π 3

Answer:
3 1
h̄ω = mω 2 x2
2 2
s
23h̄ω 3h̄ 3 3
x = = = or x = ±
mω 2 mω α α

7
 !1/2 Z
4α3 ∞ 2
P =2 √ 3 x2 e−αx dx
π α

2
y y dy
x= √ x2 = dx = √
α α α
α3/2 1 Z ∞ 2 −y2
P = (2)(2) √ √ y e dy
π α3/2 3
4 Z ∞ 2 −y2
=√ √ y e dy
π 3
10. The normalized wavefunction and energy for a harmonic oscillator of mass m in its
second excited quantum state are given by
1/4
α 5

2 /2
ψ2 (x) = (2αx2 − 1)e−αx E2 = h̄ω
4π 2
where α = mω/h̄, with ω being the natural angular frequency of the oscillator.
Recalling that the potential energy function for a harmonic oscillator is given by
V (x) = 1/2 mω 2 x2 , calculate an expression for the probability that an oscillator in
its second excited state is found in the tunneling region. A numerical answer is not
required, and you should leave your final expression in terms of exponentials and the
complimentary error function [erfc(x)].
Answer: !1/2  1/2
5 1 2 2 5h̄ 5
h̄ω = mω x x=± =±
2 2 mω α
1/2 Z ∞
α

2
P =2 √ (2αx2 − 1)2 e−αx dx
4π 5/α

√ y2 dy
y= αx x2 = dx =
α α
1 Z∞ 2 2 1 √ √
P = √ √ (2y − 1)2 e−y dy = √ [e−5 (51/2 + 2 × 53/2 ) + π erfc( 5)]
π 5 π
11. Consider a particle of mass m confined to move on the perimeter of a ring of radius R.
Evaluate < Lz > for the particle if the particle’s wavefunction is given by

(a) e−iφ ;
Answer:
1 Z 2π iφ h̄ ∂ −iφ
hLz i = e e dφ
2π 0 i ∂φ
h̄ Z 2π
=− dφ = −h̄
2π 0

8
 (b) e2iφ ;
Answer:
1 Z 2π −2iφ h̄ ∂ 2iφ
hLz i = e e dφ
2π 0 i ∂φ
2h̄ Z 2π
= dφ = 2h̄
2π 0
(c) cos φ.
Answer: Z 2π
2 h̄ ∂
hLz i = N cos φ cos φdφ
0 i ∂φ
N 2 h̄ Z 2π
=− cos φ sin φdφ = 0
i 0

12. In spherical polar coordinates the operator corresponding to the square of the angular
momentum L̂2 is given by

1 ∂2
!
2 2 1 ∂ ∂
L̂ = −h̄ sin θ +
sin θ ∂θ ∂θ sin2 θ ∂φ2

∂2 1 ∂2
!
2 cos θ ∂
= −h̄ + 2+
sin θ ∂θ ∂θ sin2 θ ∂φ2
Show that the spherical harmonic Y10 (θ, φ) given in Eq. (7.61) on page 131 of the text
is an eigenfunction of L̂2 .
Answer: Y10 (θ, φ) is independent of φ, and we need only consider the θ dependence of
the angular momentum operator. We can also ignore all constants. Then

∂2
!
cos θ ∂
+ 2 cos θ = − cos θ − cos θ = −2 cos θ.
sin θ ∂θ ∂θ

13. Consider a particle of mass m confined to move on the perimeter of a ring of radius R
h̄2 d2
with associated Hamiltonian operator Ĥ = − with the moment of inertia given
2I dφ2
by I = mR2 and the coordinate φ in the range 0 ≤ φ < 2π. Show that the wavefunction
ψ(φ) = A sin φ satifies the time-independent Schrödinger equation for the system with
A the normalization constant. Use the wavefunction to evaluate an expression for
hL2z i − hLz i2 . The operator corresponding to the square of the z-component of the
d2
angular momentum of the system is just the square of L̂z ; i.e. L̂2z = −h̄2 2 .
dφ
Answer:
ψ = A sin φ ψ 0 = A cos φ ψ 00 = −A sin φ
h̄2 d2 ψ h̄2 h̄2
− = A sin φ = ψ
2I dφ2 2I 2I

9
 Z 2π " #2π
2 2 2 φ 1
A sin φ dφ = A − sin 2φ
0 2 4 0
1
= πA2 = 1 A= √
π
1 Z 2π h̄ d 1 Z 2π
hLz i = sin φ sin φ dφ = sin φ cos φ dφ = 0
π 0 i dφ π 0
1 2 Z 2π d2 h̄2 Z 2π 2
hL2z i = − h̄ sin φ 2 sin φ dφ = sin φ dφ = h̄2
π 0 dφ π 0
hL2z i − hLz i2 = h̄2

14. Consider a particle of mass m confined to move on the perimeter of a ring of radius R
h̄2 d2
with associated Hamiltonian operator Ĥ = − with the moment of inertia given
2I dφ2
by I = mR2 and the coordinate φ in the range 0 ≤ φ < 2π. Show that the wavefunction
ψ(φ) = A(e3iφ + e−3iφ ) satisfies the time-independent Schrödinger equation for the
system with A the normalization constant. Normalize the wavefunction, and use the
result to evaluate an expression for hLz i for the particle.
Answer:

ψ 0 (φ) = A(3ie3iφ − 3ie−3iφ ) ψ 00 (φ) = A(−9e3iφ − 9e−3iφ ) = −9ψ(φ)

h̄2 00 9h̄2
Ĥψ = − ψ (φ) = ψ(φ)
2I 2I
Z 2π Z 2π
A2 dφ (e−3iφ + e3iφ )(e3iφ + e−3iφ ) = A2 dφ (1 + 1 + e6iφ + e−6iφ )
0 0
1
= 4πA2 = 1 A= √
2 π
1 Z 2π h̄ d 3iφ
hLz i = dφ (e−3iφ + e3iφ ) (e + e−3iφ )
4π 0 i dφ
3h̄ Z 2π
= dφ (1 − 1 + e6iφ − e−6iφ ) = 0
4π 0
15. Consider a particle of mass m confined to move on the perimeter of a ring of radius R
h̄2 d2 L̂2z
with associated Hamiltonian operator Ĥ = − = with the moment of inertia
2I dφ2 2I
given by I = mR2 and the coordinate φ in the range 0 ≤ φ < 2π. Show that the
wavefunction ψ(φ) = A cos 5φ satisfies the time-independent Schrödinger equation for
the system with A the normalization constant. Normalize the wavefunction, and use
the result to evaluate an expression for hL2z i − hLz i2 for the particle.
Answer:
ψ 0 (φ) = −5A sin 5φ ψ 00 (φ) = −25A cos 5φ = −25ψ

10
 h̄2 25h̄2
Ĥψ = 25ψ = Eψ or E=
2I 2I
Normalization Z 2π √
A2 cos2 5φ dφ = 1 = A2 π A = 1/ π
0
1
ψ(φ) = √ cos 5φ
π
2I Z 2π h̄2 d2
hL2z i = 2IhĤi = cos 5φ − cos 5φ dφ
π 0 2I dφ2
25h̄2 Z 2π
= cos2 5φ dφ = 25h̄2
π 0
h̄ Z 2π d
hLz i = cos 5φ cos 5φ dφ
iπ 0 dφ
5h̄ Z 2π
=− cos 5φ sin 5φ dφ = 0
iπ 0
hL2z i − hLz i2 = 25h̄2

11