Problem Set: Postulates of Quantum

Mechanics
Quantum Chemistry
Sept-Dec, 2023 Marcos Becerra – Manuel Caetano

1 Postulates of Quantum Mechanics

Taken from Quantum Chemistry by Donald McQuarrie

1. Which of the following candidates for wave functions are normalizable over the indi-
cated intervals?

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a) ex /2 (−∞, ∞) b) e−x (−∞, ∞)
c) eiθ (0, 2π) d) cosh x (0, ∞)
−x
e) xe (0, ∞)
Normalize those that can be normalized. Are the others suitable wave functions?

2. Which wavefunctions are normalized over the indicated two-dimensional intervals?

a)e−(x )/2
2 +y 2
0 ≤ x < ∞; 0 ≤ y < ∞
b)e−(x+y)/2 0 ≤ x < ∞; 0 ≤ y < ∞
4 1/2
sin πx sin πy


c) ab a b
0 ≤ x ≤ a; 0 ≤ y < ∞

Normalize those that aren’t.

3. Why does ψ ∗ ψ have to be everywhere real, nonnegative, finite, and of definite value?

4. In this problem, we will prove that the form of the Schrödinger equation imposes the
condition that the first derivative of a wave function is continuous. The Schrödinger
equation is
d2 ψ 2m
+ 2 [E − V (x)] ψ(x) = 0
dx2 ℏ
If we integrate both sides from a − ϵ to a + ϵ, where a is an arbitrary value of x and ϵ
is infinitesimally small, then we have

2m a+ϵ
Z
dψ dψ
− = 2 [V (x) − E] ψ(x)dx
dx x=a+ϵ dx x=a−ϵ ℏ a−ϵ

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 Now show that dψ/dx is continuous if V (x) is continuous. Suppose now that V (x) is
not continuous at x = a, as in
Show that
dψ dψ 2m
− = (Vl + Vr − 2E) ψ(a)ϵ
dx x=a+ϵ dx x=a−ϵ ℏ2
so that dψ/dx is continuous even if V (x) has a finite discontinuity. What if V (x)
has an infinite discontinuity, as in the problem of a particle in a box? Are the wave
functions’ first derivatives continuous at the box’s boundaries?

5. Determine whether the following functions are acceptable as state functions over the
indicated intervals.
a) x1 (0, ∞) b) e−2x sinh x (0, ∞)
c) e−x cos x (0, ∞) d) ex (−∞, ∞)
e) e−x sinh x (0, ∞)

6. Consider the linear differential equation

a(x)y ′′ (x) + b(x)y ′ (x) + c(x)y(x) = 0

where y ′′ (x) and y ′ (x) are standard notation for d2 y/dx2 and dy/dx, respectively. Show
that if y1 (x) and y2 (x) are each solution to the above differential equation, then so is
y(x) = c1 y1 (x) + c2 y2 (x), where c1 and c2 are constants.

7. Calculate the values of σE2 = ⟨E 2 ⟩ − ⟨E⟩2 for a particle in a box in the state described
by
 1/2
630
ψ(x) = x2 (a − x)2 0≤x≤a
a9

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 8. Consider a free particle constrained to move over the rectangular region 0 ≤ x ≤ a, 0 ≤
y ≤ b. The energy eigenfunctions of this system are
 1/2 
4 nx πx ny πy nx = 1, 2, 3, . . .
ψnx ,ny (x, y) = sin sin
ab a b ny = 1, 2, 3, . . .

The Hamiltonian operator for this system is

ℏ2 ∂2 ∂2
 
Ĥ = − +
2m ∂x2 ∂y 2

Show that if the system is one of its eigenstates, then

σE2 = E 2 − ⟨E⟩2 = 0

9. The momentum operator in two dimensions is

 
∂ ∂
P̂ = −iℏ i +j
∂x ∂y

Using the wave function given in Problem 8, calculate the value of ⟨p⟩ and then

σp2 = p2 − ⟨p⟩2

Compare your result with σp2 in the one-dimensional case.

10. Suppose that a particle in a two-dimensional box (cf. Problem 8) is in the state
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ψ(x, y) = x(a − x)y(b − y)
(a5 b5 )1/2

Show that ψ(x, y) is normalized, and then calculate the value of ⟨E⟩ associated with
the state described by ψ(x, y).

11. Evaluate the commutator [A, B], where A and B are given below.

 B̂
d2
a) dx2
x
d d
b) dx
−x dx
+x
Rx d
c) 0
dx dx
d2 d
d) dx2
−x dx
+ x2

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12. Show that
h i
L̂x , L̂y = iℏL̂z
h i
L̂y , L̂z = iℏL̂x

and
h i
L̂z , L̂x = iℏL̂y

What do these expressions say about the ability to simultaneously measure the com-
ponents of angular momentum?
h i h i h i
13. Consider a particle in a two-dimensional box. Determine X̂, Pˆy , X̂, Pˆx , Ŷ , Pˆy ,
h i
and Ŷ , Pˆx

14. Can an electron’s position and kinetic energy be measured simultaneously to arbitrary
precision?

15. Using the result of Problem 14, what are the ”uncertainty relationships” ∆x∆py and
∆y∆px equal to?

16. Which of the following operators is Hermitian: d/dx, i d/dx, d2 /dx2 , i d2 /dx2 , x d/dx,
and x? Assume that the functions on which these operators operate are appropriately
well-behaved at infinity.

17. Show that if  is Hermitian, then  − ⟨a⟩ is Hermitian. Show that the sum of two
Hermitian operators is Hermitian.

18. Show that if  is Hermitian, then:

Z Z
 ψ B̂ψdx = ψ ∗ ÂB̂ψdx
∗ ∗

19. Show that

2
ψ0 (x) = π −1/4 e−x /2
 1/4
4 2
ψ1 (x) = xe−x /2
π
2
ψ2 (x) = (4π)−1/4 2x2 − 1 e−x /2

are orthonormal over the interval −∞ < x < ∞.


20. Show that the set of functions (2/a)1/2 cos(nπx/a) , n = 0, 1, 2, . . . is orthonormal
over the interval 0 ≤ x ≤ a.

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21. Express the orthonormality of the set of functions {ψn (x)} in Dirac notation. Ex-
P
press the eigenfunction expansion ϕ(x) = n cn ψn (x) and the coefficients cn in Dirac
notation.

22. A general state function, expressed in the form of a ket vector |ϕ⟩, can be written as a
superposition of the eigenstates |1⟩ , |2⟩ , . . . of an operator  with eigenvalues a1 , a2 , . . .
(in other words, Â |n⟩ = an |n⟩):
X
|ϕ⟩ = c1 |1⟩ + c2 |2⟩ + · · · = cn |n⟩
n

Show that cn = ⟨n|ϕ⟩. This quantity is called the amplitude of measuring an if a

measurement of  is made in the state |ϕ⟩. The probability of obtaining an is c∗n cn .
Show that |ϕ⟩ can be written as
X
|ϕ⟩ = |n⟩ ⟨n|ϕ⟩
n

Similarly, the corresponding bra vector of |ϕ⟩ can be written in terms of the corre-
sponding bra vectors of the |n⟩ as
X
⟨ϕ| = c∗n ⟨n|
n

Show that c∗n = ⟨ϕ|n⟩. Show that ⟨ϕ| can be written as

X
⟨ϕ| = ⟨ϕ|n⟩ ⟨n|
n

Now show that if ⟨ϕ| is normalized, then

⟨ϕ|ϕ⟩ = 1 = ⟨ϕ|n⟩ ⟨n|ϕ⟩

and use this result to argue that

X
|n⟩ ⟨n| = 1
n

is a unit operator.

23. Using the orthogonality of the set {sin(nπx/a)} over the interval 0 ≤ x ≤ a, show that
if
∞
X nπx
f (x) = bn sin
n=1
a

then
Z a
2 nπx
bn = f (x) sin dx n = 1, 2, . . .
a 0 a

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 Use this to show that the Fourier expansion of f (x) = x, 0 ≤ x ≤ a, is
∞
2a X (−1)n+1 nπx
x= sin
π n=1 n a

24. If ψn is an eigenfunction of the time-independent Schrödinger equation, then

Ψn (x, t) = ψn (x)e−iEn t/ℏ

Show that if ψm (x) and ψn (x) are both stationary states of Ĥ, then the state

Ψ(x, t) = cm ψm (x)e−iEm t/ℏ + cn ψn (x)e−iEn t/ℏ

satisfies the time-dependent Schrödinger equation.

25. What is the normalization constant for Ψ(x, t) = N −iEn t/ℏ

P
n=1 ψn (x)e if the ψn (x) are
orthonormalized?

26. Derive an expression for the average position of a particle in a box in a state described
by
 1/2  1/2
1 −iE2 t/ℏ 2πx 1 3πx
Ψ(x, t) = e sin + e−iE3 t/ℏ sin
a a a a

With what frequency does the particle oscillate about the midpoint of the box?

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27. Consider a particle moving in the potential energy

whose mathematical form is


0 x<0
V (x) =
V0 x > 0

where V0 is a constant. Show that if E > V0 , then the solutions to the Schrödinger
equation in the two regions (1 and 2) are

ψ1 (x) = Aeik1 x + Be−ik1 x x<0 (1)

and
ψ2 (x) = Ceik2 x + De−ik2 x x>0 (2)
where ! " #
2mE 1/2 2m(E − V0 ) 1/2
k1 = and k2 = (3)
ℏ2 ℏ2

eikx represents a particle traveling to the right and e−ikx represents a particle traveling
to the left. The physical problem we wish to set up is a particle of energy E traveling
to the right and incident on a potential height barrier V0 . If we wish to exclude the
case of a particle traveling to the left in the region 2, we set D = 0 in equation 2.
The squares of the coefficients in equations 1 and 2 represent the probability that
the particle travels in a certain direction in a given region. For example, |A|2 is the
probability that the particle travels with momentum +ℏk1 in the region x < 0. If
we consider many particles, N0 , instead of just one, then we can interpret |A|2 N0 to
be the number of particles with momentum ℏk1 in the region x < 0. The number of
these particles that pass a given point per unit of time is given by v|A|2 N0 , where the
velocity v is given by ℏk1 /m. Now apply the conditions that ψ(x) and dψ/dx must be
continuous at x = 0 (see Problem 4) to obtain

A+B =C

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and
k1 (A − B) = k2 C
Now, define a quantity
ℏk1 |B|2 N0 /m |B|2
r= =
ℏk1 |A|2 N0 /m |A|2
and show that  2
k1 − k2
r=
k1 + k2
Similarly define !
ℏk2 |C|2 N0 /m k2 |C|2
t= =
ℏk1 |A|2 N0 /m k1 |A|2
and show that
4k1 k2
t=
(k1 + k2 )2
The symbols r and t stand for reflection and transmission coefficients, respectively.
Give a physical interpretation of these designations. Show that r + t = 1. Would you
have expected the particle to have been reflected even though its energy, E, is greater
than the barrier height, V0 ? Show that r → 0 and t → 1 as V0 → 0.