Chemistry 432

Problem Set 3
Spring 2018
Solutions

1. Consider a particle of mass m with quantum number n moving in a one-dimensional

box of length L.

(a) Find the probability of finding the particle in the left two-thirds of the box.
Answer:
2 Z 2L/3 2 nπx
P = sin dx
L 0 L
nπx L
y= dx = dy
L nπ
2 L Z 2nπ/3 2
P = sin ydy
L nπ 0
2nπ/3
2 y 1

= − sin 2y
nπ 2 4 0
2 1 4nπ
= − sin
3 2nπ 3
(b) For what value of n is this probability a maximum?
Answer:
n P
1 .804
2 .598
3 .667
4 .701
5 .639
6 .667
7 .686
8 .649
9 .667
10 .680
Maximum at n = 1.

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 (c) What is the probability as n → ∞?
Answer:
2
lim P =
n→∞ 3
the classical result.

2. For a particle of mass m in a box of length L in quantum state n, find:

(a) < x >;

Answer:
2ZL nπx nπx
hxi = sin x sin dx
L 0 L L
nπx Ly L
y= x= dx = dy
L nπ nπ
2 L 2 Z nπ
 
hxi = y sin2 ydy
L nπ 0
#nπ
2L y 2 y sin 2y cos 2y
"
= − −
(nπ)2 4 4 8 0
2
2L (nπ) L
= 2
=
(nπ) 4 2
(b) < p >;
Answer:
2ZL nπx h̄ d nπx
hpi = sin sin dx
L 0 L i dx L
h̄ 2 nπ Z L nπx nπx
= sin cos =0
iL L 0 L L
(c) < K = p2 /2m >.

−h̄2 d2
!
2ZL nπx nπx
hKi = sin 2
sin dx
L 0 L 2m dx L

2 h̄2 Z L
" 2 #
nπx nπ nπx

=− sin − sin
L 2m 0 L L L
h̄2 (nπ)2 Z L 2 nπx
= sin dx
mL L2 0 L
h̄2 n2 π 2 L
=
mL3 2
n2 π 2 h̄2
=
2mL2

2
3. Consider a one-dimensional particle of mass m confined to move in a box of length L
on a coordinate system defined so that the potential energy is given by
(
0 − L2 ≤ x ≤ L
2
V (x) =
∞ elsewhere

(a) Show that the normalized wavefunctions

1/2
2 x 1
   
ψn (x) = sin nπ + n = 1, 2, 3, . . .
L L 2
satisfy the Schrödinger equation for the particle within the box.
Answer:
h̄2 d2 ψ
− = Eψ
2m dx2
1/2
dψ 2 nπ x 1
   
= cos nπ +
dx L L L 2
1/2
d2 ψ 2 nπ x 1 nπ 2
   
2
=− ( )2 sin nπ + = −( )ψ
dx L L L 2 L
h̄2 d2 ψ n2 π 2 h̄2
− = ψ = Eψ
2m dx2 2mL2
(b) Give the appropriate boundary conditions for the system defined in part “a,” and
show that the wavefunctions given in part ‘a” satisfy the boundary conditions.
Answer:
ψ(−L/2) = ψ(L/2) = 0
1/2 1/2
2 L 1 2
    
ψ(−L/2) = sin nπ − + = sin(0) = 0
L 2L 2 L
1/2 1/2
2 L 1 2
    
ψ(L/2) = sin nπ + = sin(nπ) = 0
L 2L 2 L
(c) For a particle in the first excited state with associated wavefunction
1/2
2 x 1
   
ψ2 (x) = sin 2π +
L L 2
determine at what point or points in space the particle is most likely to be found.
Answer:
2 x 1
  
2
P2 (x) = sin 2π +
L L 2
4 2π x 1 x 1
     
P20 (x) = sin 2π + cos 2π +
L L L 2 L 2
=0 at

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 x 1 π 3π
 
2π + = or
L 2 2 2
Then
L L
x=− ,
4 4
(d) For a particle represented by the first excited state wavefunction given in part
“c,” calculate the probability that a measurement of the position of the particle
will give a result in the interval −L/2 ≤ x ≤ 0.
Answer:
2Z0 x 1
  
2
P = sin 2π + dx
L −L/2 L 2
2πx L
Let y= +π dx = dy
L 2π
π
2 L Zπ 2 1 y 1

P = sin y dy = − sin 2y
L 2π 0 π 2 4 0
1
=
2
4. The wavefunction for a particle of mass m in a box of length L defined on the interval
−L/2 ≤ x ≤ L/2 is given by
x 1
  
ψ(x) = N sin π +
L 2
where N is the normalization factor. Derive an expression for the expectation value of
the kinetic energy of the particle.
Answer: Z L/2
x 1
  
2 2
N sin π + dx = 1
−L/2 L 2
x 1 π L
 
y=π + dy = dx dx = dy
L 2 L π
Z π π
L L y 1 L

N2 sin2 y dy = N 2 − sin 2y = N 2 = 1
π 0 π 2 4 0 2
or  1/2
2 x 1
  
ψ(x) = sin π +
L L 2
h̄2 d2
Z !
∗
hT i = ψ (x) − ψ(x)dx
D 2m dx2
2h̄2 Z L/2 x 1 d2 x 1
     
=− sin π + 2
sin π + dx
2mL −L/2 L 2 dx L 2
2h̄2 π 2 Z L/2
! !
x 1
  
2
= sin π + dx
2mL L2 −L/2 L 2

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 2h̄2 π2 π 2 h̄2
! !
L

= =
2mL L2 2 2mL2
5. A particle of mass m is confined to a one-dimensional box of length L in the domain
−L/4 < x < 3L/4. Show that the wavefunction
πx π
 
ψ(x) = sin +
L 4
satisfies the time-independent Schrödinger equation for the system as well as the ap-
propriate boundary conditions.
Answer:
h̄2 d2 ψ
Ĥψ = Eψ = −
2m dx2
π πx π π2 πx π
   
ψ 0 (x) = cos + ψ 00 (x) = − 2 sin +
L L 4 L L 4
2 2 2 2
h̄ π πx π h̄ π
 
Ĥψ = sin + E =
2mL2 L 4 2mL2
ψ(−L/4) = ψ(3L/4) = 0
π −L π
 
ψ(−L/4) = sin + = sin 0 = 0
L 4 4

π 3L π
 
ψ(3L/4) = sin + = sin π = 0
L 4 4
6. The normalized wavefunction for a particle of mass m in a one-dimensional box of
length L on the domain 0 < x < L in its 4th excited energy state is given by
2 1/2 5πx
   
ψ5 (x) = sin .
L L
Calculate the probability that a measurement of the position of the particle will give
a result in the region between x = 0 and the first node of the wavefunction.
Answer:
The first node occurs at
5πx L
=π or x=
L 5
Z L/5 Z L/5
2 5πx
 
p= ψ ∗ (x)ψ(x) dx = sin2 dx
0 L 0 L
5πx L
y= dx = dy
L 5π
2 L Zπ 2
  
p= sin y dy
L 5π 0
π
2 y 1 1

= − sin 2y =
5π 2 4 0 5

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7. The normalized wavefunction for a particle of mass m in a one-dimensional box in
quantum state n on the domain −L/2 ≤ x ≤ L/2 is given by
1/2
2 x 1
   
ψn (x) = sin nπ + .
L L 2
Calculate the probability the particle is found on the interval between −L/2 and the
first node of the wavefunction.
Answer:
The first node is found at
x 1 x 1 1 1 1
   
nπ + =π + = x=L −
L 2 L 2 n n 2
2 Z L(1/n−1/2) 2 x 1
  
P = sin nπ + dx
L −L/2 L 2
x 1 L
 
y = nπ + dx = dy
L 2 nπ
2 L Zπ 2
  
P = sin y dy
L nπ 0
π
2 y 1 1

= − sin 2y =
nπ 2 4 0 n
8. A particle of mass m is confined to move in a box of length L on the domain −L/10 ≤
x ≤ 9L/10 by action of potential energy
L 9L


0 ≤x≤ −
V (x) = 10 10
∞ elsewhere


The particle is in the state with quantum number n = 2 and associated normalized
wavefunction  1/2
2 2π L
  
ψ2 (x) = sin x+ .
L L 10
Show that ψ2 (x) satisfies the appropriate boundary conditions for the system, and find
the points in space that the particle is most likely to be found.
Answer:
ψ2 (−L/10) = ψ2 (9L/10) should = 0
1/2 1/2
2 2π L L 2
    
ψ2 (−L/10) = sin − + = sin 0 = 0
L L 10 10 L
1/2 1/2
2 2π 9L L 2
    
ψ2 (9L/10) = sin + = sin 2π = 0
L L 10 10 L
2 2π L
  
P (x) = sin2 x+
L L 10

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 4 2π 2π L 2π L
     
P 0 (x) = sin x+ cos x+ =0
L L L 10 L 10
at
2π L π 3π
 
x+ = ,
L 10 2 2
or
3L 13L
x= ,
20 20
9. A particle of mass m in a box of length L, defined on the domain −L/5 ≤ x ≤ 4L/5,
occupies its first excited energy state with associate normalized wavefunction
1/2
2 2π L
   
ψ2 (x) = sin x+ .
L L 5
Let xn be the coordinate of the node of the wavefunction, xL and xU be the coordinates
where the particle is most likely to be found such that xL < xU . Determine the locations
xn , xL and xU , and calculate the probability that a measurement of the coordinate of
the particle gives a result in the range xL ≤ x ≤ xn .
Answer:
2π L
  
sin x+ =0
L 5
when
2π L 3L
 
xn + =π or xn =
L 5 10
Now
2 2 2π L
    
P (x) = sin x+
L L 5
and
8π 2π L 2π L
       
0
P (x) = sin x+ cos x+
L2 L 5 L 5
2π L
  
P 0 (x) = 0 when cos x+ =0
L 5
or
2π L π 3π
 
x+ = ,
L 5 2 2
and
L 11L
xL = xU =
20 20
Z 3L/10
2 2π L
  
P = sin2 x+ dx
L L/20 L 5
2π L 2π
 
y= x+ dy = dx
L 5 L
π
2 L Zπ 1 y 1 1

2
P = sin y dy = − sin 2y =
L 2π π/2 π 2 4 π/2 4

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10. A quantum particle of mass m is confined to a one-dimensional box on the domain
−L/2 ≤ x ≤ L/2. The normalized solutions to the Schrödinger equation for the
particle are given by
1/2
2 x 1
   
ψn (x) = sin nπ + , n = 1, 2, . . .
L L 2
Let x1 be the first node of the wavefunction for n = 3 and x2 be the second node of the
wavefunction for n = 3. Calculate the probability that a measurement of the position
of the particle in the state defined by n = 3 gives a result in the range x1 ≤ x ≤ x2 .
Answer:
x1 1 L
 
x1 : 3π + =π x1 = −
L 2 6
x2 1 L
 
x2 : 3π + = 2π x2 =
L 2 6
Z L/6
2 x 1
  
P = sin2 3π + dx
L −L/6 L 2
x 1 3π
 
y = 3π + dy = dx
L 2 L
2 L Z 2π 2
P = sin y dy
L 3π π
2π
2 y 1 2 π 1

= − sin 2y = =
3π 2 4 π 3π 2 3
11. Calculate < xy 2 > for a particle of mass m having quantum numbers nx and ny in a
two-dimensional box whose sides have lengths Lx and Ly .
Answer:
2 2 2 Z Lx Z Ly
nx πx 2 ny πy
hxy i = dx dy xy 2 sin2 sin
Lx Ly 0 0 Lx Ly
2 2 Z Lx 2 nx πx
Z Ly
ny πy
= dx x sin dy y 2 sin2
Lx Ly 0 Lx 0 Ly
Lx 2 Z Ly ny πy
dy y 2 sin2
2 Ly 0 Ly
where we have used the result found in Problem 2a. Using
ny πy Ly
z= dy = dz
Ly ny π

Then !3 Z
Lx 2 Ly ny π
2
hxy i = dzz 2 sin2 z
2 Ly ny π 0

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 #ny π
Lx 2L2y z3 z2 1
" !
z cos 2z
= 3
− − sin 2z −
2 (ny π) 6 4 8 4 0
" #
1 1 1
= Lx L2y −
2 3 2(ny π)2

12. The normalized wavefunctions for a particle of mass m in a one-dimensional box of

length L on the domain 0 ≤ x ≤ L are given by the set
1/2
2 nπx

ψn (x) = sin n = 1, 2, 3, . . .
L L
Calculate < xyz > for a particle of mass m having quantum numbers nx , ny and nz in
a three-dimensional box whose sides have lengths Lx , Ly and Lz .
Answer:
In one dimension
2ZL nπx
hxi = x sin2 dx
L 0 L
nπx Ly L
y= x= dx = dy
L nπ nπ
2 L 2 Z nπ
 
hxi = y sin2 y dy
L nπ 0
#nπ
2L y 2 1
"
1 L
= 2
− y sin(2y) − cos(2y) =
(nπ) 4 4 8 0
2
In three dimensions

Ψnx ,ny ,nz (x, y, z) = ψnx (x)ψny (y)ψnz (z)

so that
Lx Ly Lz
hxyzi = hxihyihzi =
8
13. The normalized wavefunction for a quantum particle of mass m in a one-dimensional
box of length L on the domain 0 ≤ x ≤ L with quantum number n is given by
1/2
2 nπx

ψn (x) = sin
L L
Consider a particle of mass m in a two-dimensional box whose sides are of lengths Lx
and Ly ; i.e. the domain is 0 ≤ x ≤ Lx and 0 ≤ y ≤ Ly . Suppose the quantum state of
the particle is defined by the quantum numbers in the x and y Cartesian directions by
nx = 1 and ny = 2. Calculate hx2 yi for the particle.
Answer:
hx2 yi = hx2 ihyi

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 1/2
Z Lx 
2 πx 2 2 1/2 πx 2 Z Lx 2 2 πx
 
2
hx i = sin x sin dx = x sin dx
0 Lx Lx Lx Lx Lx 0 Lx
πx Lx Lx
z= x= z dx = dz
Lx π π
3 Z π
2 Lx L2x

hx2 i = z 2 sin2 z dz = [2π 3 − 3π]
Lx π 0 6π 3
2 Z Ly 2πy
hyi = y sin2 dy
Ly 0 Ly
2πy Ly Ly
z= y= z dy = dz
Ly 2π 2π
2 Z 2π 2
2 Ly 2 Ly 4π 2 Ly
 
2
hyi = z sin z dz = =
Ly 2π 0 Ly 2π 4 2
Ly L2x
hx2 yi = [2π 3 − 3π]
2 6π 3

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