Chemistry 432

Problem Set 2
Spring 2018
Solutions

1. By showing
f (x, t) = Aei(kx−ωt)
satisfies the classical wave equation

∂ 2f 1 ∂ 2f
= .
∂x2 v 2 ∂t2
determine a relation between ω, k and v.
Answer:
∂f
= ikAei(kx−ωt)
∂x
∂ 2f
= −k 2 Aei(kx−ωt)
∂x2
∂f
= −iωAei(kx−ωt)
∂t
∂ 2f
2
= −ω 2 Aei(kx−ωt)
∂t
Then
∂ 2f 1 ∂ 2f
=
∂x2 v 2 ∂t2
if
ω
=v
k
2. Consider the Schrödinger equation in time dependent form
∂Ψ
ih̄ = ĤΨ
∂t
where
h̄2 ∂ 2
Ĥ = − + V (x).
2m ∂x2

1
 Show that if we write
Ψ(x, t) = ψ(x)e−iEt/h̄
we obtain
Ĥψ = Eψ
where E is the energy of the system.
Answer:
∂Ψ(x, t) ∂
ih̄ = ih̄ψ(x) e−iEt/h̄ = Eψ(x)e−iEt/h̄
∂t ∂t
ĤΨ(x, t) = e−iEt/h̄ Ĥψ(x)
Then
e−iEt/h̄ Ĥψ(x) = e−iEt/h̄ Eψ(x)
or
Ĥψ(x) = Eψ(x)

3. The momentum operator is defined by

h̄ d
p̂ = .
i dx
Determine which of the following functions are eigenfunctions of the momentum oper-
ator (k is a constant):

(a) sin kx
Answer:
h̄ d h̄
p̂ sin kx = sin kx = k cos kx 6= const. sin kx
i dx i
Not an eigenfunction
(b) eikx
Answer
h̄ d ikx
p̂eikx = e = h̄keikx
i dx
Eigenfunction
(c) x4
Answer:
h̄ d 4 h̄ 3
p̂x4 = x = 4x 6= const.x4
i dx i
Not an eigenfunction

4. If 20 coins weigh 10 grams each, 30 coins weigh 4 grams each and 10 coins weigh 8
grams each, compute the average weight, < w >, of the 60 coins. Also compute < w2 >
and < w >2 . If all the 60 coins weighed 5 grams each, find < w >, < w2 > and < w >2 .
Answer:

2
 (a)
20 × 10 + 30 × 4 + 10 × 8
hwi = g = 6.67g
60
20 × 102 + 30 × 42 + 10 × 82 2
hw2 i = g = 52g2
60
hwi = 44.5g2
2

(b)
hwi = 5g
hw2 i = hwi2 = 25g2
5. The wavefunction for a quantum particle of mass m confined to move in the domain
0 ≤ x ≤ L is given by
ψ(x) = N sin(4πx/L)
where N is the normalization factor.
(a) Normalize the wavefunction.
Answer: Z L 4πx
 
N2 sin2 dx = 1
0 L
4πx L L
y= x= y dx = dy
L 4π 4π
LN 2 Z 4π 2 L 4π L
sin ydy = N 2 = N2 = 1
4π 0 4π 2 2
 1/2
2
N=
L
 1/2
2 4πx
 
ψ(x) = sin
L L
(b) Calculate the expectation value of x for the particle.
Answer:
2ZL 4πx 4πx
hxi = sin x sin dx
L 0 L L
4πx L L
y= x= y dx = dy
L 4π 4π
2 L 2 Z 4π
 
hxi = y sin2 ydy
L 4π 0
#4π
2L y 2 y sin 2y cos 2y
"
= − −
(4π)2 4 4 8 0
2
2L (4π) L
= 2
=
(4π) 4 2

3
 (c) Calculate the expectation value of p for the particle.
Answer:
2ZL 4πx h̄ d 4πx
hpi = sin sin dx
L 0 L i dx L
2h 4π Z L 4πx 4πx
= sin cos =0
iL L 0 L L
(d) Calculate the expectation value of the kinetic energy of the particle.
Answer:
h̄2 d2
!
2ZL 4πx 4πx
hT i = sin − 2
sin dx
L 0 L 2m dx L
2
d2 4πx 4π 4πx

2
sin =− sin
dx L L L
2 h̄2 4π
2 Z L
4πx

hT i = sin2 dx
L 2m L 0 L
2 2
2 L 16h̄ π 16h̄2 π 2
= =
L 2 2mL2 2mL2
(e) Calculate the probability of finding the particle in the region from x = 0 to
x = L/4.
Answer:
2 Z L/4 2 4πx
P = sin dx
L 0 L
2 L Zπ 2
= sin ydy
L 4π 0
2 L π 1
= =
L 4π 2 4
6. The state of a one-dimensional quantum system is represented by the wavefunction

ψ(x) = N sin(3πx)

for 0 < x < 1 with N being the normalization factor. Calculate the probability that a
measurement of the position of the particle will give a result in the range 2/3 ≤ x < 1.
Answer: Z 1
2
N sin2 3πx dx = 1
0
1
y = 3πx dx = dy
3π
3π
N 2 Z 3π 2 N2 y 1 N2

sin y dy = − sin 2y = =1
3π 0 3π 2 4 0 2
or √
N= 2

4
 Z 1 3π
2 Z 3π 2 2 y 1

2
P =2 sin 3πx dx = sin y dy = − sin 2y
2/3 3π 2π 3π 2 4 2π

2 π 1
= = .
3π 2 3
7. The wavefunction for a one-dimensional particle of mass m confined to move on the
interval 0 ≤ x ≤ π is given by

ψ(x) = N sin(7x)

where N is the normalization constant. Normalize the wavefunction to calculate N ,

and then calculate the expectation value of the kinetic energy of the particle.
Answer: Z π
N2 sin2 7x dx = 1
0
dy
y = 7x dx =
7
7π
N 2 Z 7π 2 N2 y 1 N 2 7π π

sin y dy = − sin 2y = = N2 = 1
7 0 7 2 4 0 7 2 2
 1/2  1/2
2 2
N= and ψ(x) = sin(7x)
π π
h̄2 d2
!
2Zπ
hT i = sin 7x − sin 7x dx
π 0 2m dx2
49h̄2 Z π 2
= sin 7x dx
πm 0
49h̄2 π 49h̄2
= =
πm 2 2m
8. The wavefunction for a harmonic oscillator of mass m and natural frequency ω is given
by
ψ(x) = exp(−mωx2 /2h̄).
Normalize this wavefunction and evaluate hxi. Note the domain of this problem is
−∞ < x < ∞.
Answer: !1/2
Z ∞
2 2 2 πh̄
N exp(−mwx /h̄) dx = N =1
−∞ mω
1/4
mω

N=
πh̄
1/2 Z ∞
mω

hxi = x exp(−mωx2 /h̄) dx = 0
πh̄ −∞

5
 9. The wavefunction for a quantum system on the domain −∞ < x < ∞ is given by
2
ψ(x) = N e−ax , where a is a constant and N is the normalization constant. Normalize
the wavefunction and calculate an expression for the expectation value of x2 ; i.e. hx2 i.
Answer: Z ∞ Z ∞
2
2
|ψ| dx = N 2
e−2ax dx
−∞ −∞
1/2
π

= N2 =1
2a
1/4
2a

N=
π
and 1/4
2a

2
ψ(x) = e−ax
π
Z ∞
hx2 i = ψ ∗ (x)x2 ψ(x)dx
−∞
1/2 Z ∞
2a

2 2
= e−ax x2 e−ax dx
π −∞

2a 1/2 Z ∞
1/2
π 1/2
!
2a 1
  
−2ax2
= x2 e dx = =
π −∞ π 2(2a)3/2 4a

10. A particle of mass m is confined to move in one dimension on the domain 0 ≤ x < ∞,
and its quantum state is associated with the wavefunction ψ(x) = N xe−ax where N
is the normalization and a is a constant having units of inverse length. Normalize the
wavefunction and derive an expression for h1/xi for the particle.
Answer Z ∞
2! N2
N2 x2 e−2ax dx = N 2 = =1
0 (2a)3 4a3
N = 2a3/2
Z ∞
1 1 −ax
 
= 4a3 xe−ax xe dx
x 0 x
Z ∞
1
= 4a3 xe−2ax dx = 4a3 =a
0 (2a)2
11. The ground-state wavefunction for a quantum particle of mass m defined on the domain
2
0 ≤ x < ∞ is given by ψ(x) = N x e−ax , where a is a constant having units of inverse
length squared and N is the normalization constant. Derive an expression for hx−2 i
for the particle.
Answer: √
2
Z ∞
2 −2ax2 21 π 2(2a)3/4
N x e dx = N = 1 N =
0 4 (2a)3/2 π 1/4

6
 4(2a)3/2 Z ∞ −2ax2
hx−2 i = √ e dx
π 0
√
4(2a)3/2 1 π
= √ √ = 4a
π 2 2a
12. The state of a one-dimensional quantum particle of mass m on the interval 0 ≤ x < ∞
is represented by the wavefunction

ψ(x) = N xe−ax

where N is the normalization constant and a is a constant having units of inverse

length. Normalize the wavefunction and use the normalized wavefunction to determine
the expectation value of the linear momentum p of the particle.
Answer: Z ∞ Z ∞
2 N2
|ψ(x)|2 dx = N 2 x2 e−2ax dx = N 2 = =1
0 0 (2a)3 4a3
N = 2a3/2
Z ∞ Z ∞
∗ h̄ d −ax
hpi = ψ (x) p̂ ψ(x) dx = 4a 3
xe−ax xe dx
0 0 i dx
h̄ Z ∞ −ax −ax
= 4a3 xe [e − axe−ax ]dx
i 0
Z ∞ Z ∞
h̄
= 4a3 [ xe−2ax dx − a x2 e−2ax dx]
i 0 0
" #
3 h̄ 1 2a 3 h̄ 1 1
 
= 4a − = 4a − =0
i (2a)2 (2a)3 i 4a2 4a2
13. A one-dimensional particle of mass m occupies the interval 0 ≤ x < ∞ in a state
defined by the wavefunction
ψ(x) = N xe−ax
where N is the normalization constant and a is a constant having units of inverse
length. Normalize the wavefunction, and use the normalized wavefunction to calculate
the expectation value of the kinetic energy hT i of the particle.
Answer:
2
Z ∞
2 −2ax 2 2! N2
N xe dx = N 3
= 3 =1 N = 2a3/2
0 (2a) 4a
h̄2 d2
Z ∞ !
∗
hT i = ψ (x) − ψ(x) dx
0 2m dx2
h̄2 3 Z ∞ −ax d2 −ax
=− 4a xe xe dx
2m 0 dx2
d d −ax d −ax
xe = [e − axe−ax ] = −2ae−ax + a2 xe−ax
dx dx dx
7
 h̄2 3 Z ∞ Z ∞
hT i = 4a [ 2axe−2ax dx − a2 x2 e−2ax dx]
2m 0 0

2h̄2 a3 1 1 h̄2 a2
 
= − =
m 2a 4a 2m
14. The unnormalized wavefunction for a quantum particle on the domain 0 ≤ x < ∞ is
given by
2
ψ(x) = N xe−ax
where N is the normalization and a is a constant having units of the square of the
inverse length. Calculate the expectation value of x2 for the particle.
Answer:
#1/2
π 1/2 (2a)3/2
Z ∞ "
2 2 −2ax2 21
N x e dx = N =1 N =2
0 4 (2a)3/2 π 1/2

(2a)3/2 Z ∞
" #
2 2
2
hx i = 4 1/2
x e−ax x2 x e−ax dx
π 0

(2a)3/2 Z ∞ 4 −2ax2 (2a)3/2 3π 1/2

#" " #
3
=4 1/2
xe dx = 4 1/2 5/2
=
π 0 π 8(2a) 4a