Problem Set III

Quantum Chemistry
Feb-Jun 2024 Marcos Becerra and Manuel Caetano

1 Schrödinger Equation
Taked from Quantum Chemistry by Donald McQuarrie

1. Evaluate g = Âf ,where  and f are given below:

 f
(a)SQRT x4
d3
(b) dx3
+ x3 e−ax
R1
(c) 0 dx x3 − 2x + 3
∂2 ∂2 ∂2
(d) ∂x2
+ ∂y 2
+ ∂z 2
x3 y 2 z 4

2. Determine whether the following operators are linear or non-linear:

(a)Âf (x) = SQRf (x) [squaref (x)]
(b)Âf (x) = f ∗ (x) [form the complex conjugate of f (x)]
(c)Âf (x) = 0 [multiply f (x) by zero]
(d)Âf (x) = [f (x)]−1 [take the reciprocal of f (x)]
(e)Âf (x) = f (0) [evaluate f (x) at x = 0 ]
(f )Âf (x) = ln f (x) [take the logarithm of f (x)]
3. In each case:

• Show that f (x) is an eigenfunction of the operator given.

• Find the eigenvalue.

1
 Â f
d2
(a) dx2
cos ωx
d
(b) dt eiωt
d2 d
(c) dx2
+ 2 dx +3 eαx
∂
(d) ∂y x2 e6y

4. Show that (cos ax)(cos by)(cos cz) is an eigenfunction of the operator,

∂2 ∂2 ∂2
∇2 = + +
∂x2 ∂y 2 ∂z 2
which is called the Laplacian operator.

5. Write out the operator Â2 for  =

d2 d d2 d
(a) (b) +x (c) − 2x +1
dx2 dx dx2 dx
Hint: Include f (x) before carrying out the operations.

6. Determine whether or not the following pairs of operators commute.

 B̂
d d2 d
(a) dx dx2
+ 2 dx
d
(b) x dx
(c) SQR SQRT
∂ ∂
(d) ∂x ∂y

7. If we operate on the particle-in-a-box wave functions with the momentum operator, we find
nπx ∂  nπx 
P̂ B sin = −iℏB sin
a ∂x a
iℏnπ nπx
=− B cos
a a
Note that this is not an eigenvalue equation, so we say that the momentum of a particle in
a box does not have a fixed, definite value. Although the particle does not have a definite
momentum, we can use the classical equation E = p2 /2m to define formally some effective
momentum. Using Equation
h2 n2
En = n = 1, 2, . . .
8ma2
for E, show that p = nh/2a and that the de Broglie wavelengths associated with these
momenta are λ = h/p = 2a/n. Show that this last equation says that an integral number
of half-wavelengths fit into the box or that Figure 1 corresponds to standing de Broglie or
matter waves.

2
Figure 1: The energy levels, wave functions (a), and probability densities (b) for the particle in a
box..

8. We applied the equations for a particle in a box to the π electrons in butadiene. This simple
model is called the free-electron model. Using the same argument, show that the length
of hexatriene can be estimated to be 867 pm. Show that the first electronic transition is
predicted to occur at 2.8 × 104 cm−1 . (Remember that hexatriene has six π electrons.)

9. Prove that if ψ(x) is a solution to the Schrödinger equation, then any constant times ψ(x) is
also a solution.

10. Show that the probability associated with the state ψn for a particle in a one-dimensional
box of length a obeys the following relationships:
( 1
4 n even
Prob (0 ≤ x ≤ a/4) = Prob (3a/4 ≤ x ≤ a) = n−1
(−1) 2
1
4 − 2πn n odd

and
1
(
4 n even
Prob (a/4 ≤ x ≤ a/2) = Prob (a/2 ≤ x ≤ 3a/4) = n−1
(−1) 2
1
4 + 2πn n odd

11. Show that

a
⟨x⟩ =
2
for all the states of a particle in a box. Is this result physically reasonable?

12. Show that ⟨p⟩ = 0 for all states of a one-dimensional box of length a.

13. Show that  1/2

σx = x2 − ⟨x⟩2

3
 for a particle in a box is less than a, the width of the box, for any value of n. If σx is the
uncertainty in the position of the particle, could σx ever be larger than a?

14. Using the trigonometric identity

1 1
sin α sin β = cos (α − β) − cos (α + β)
2 2
show that the particle-in-a-box wave functions satisfy the relation
Z a
ψn∗ (x)ψm (x) dx = 0 m= ̸ n
0

(The asterisk in this case is superfluous because the functions are real.) If a set of functions
satisfies the above integral condition, we say that the set is orthogonal and, in particular,
that ψm (x) is orthogonal to ψn (x). If, in addition, the functions are normalized, then we say
that the set is orthonormal.

15. Prove that the set of functions

ψn (x) = (2a)−1/2 eiπnx/a n = 0, ±1, ±2, . . .

is orthonormal over the interval −a ≤ x ≤ a. A compact way to express orthonormality in

the ψn is to write Z a
∗
ψm (x)ψn (x) dx = δmn
−a
The symbol δmn is called a Kronecker delta and is defined by

1 if m = n
δmn =
0 if m ̸= n

16. Calculate ⟨x⟩ and x2 for the n = 2 state of a particle in a one-dimensional box of length a.
Show that 1/2
a 4π 2

σx = −2
4π 3

17. Calculate ⟨p⟩ and p2 for the n = 2 state of a particle in a one-dimensional box of length a.
Show that
h
σp =
a
18. Consider a particle of mass m in a one-dimensional box of length a. Its average energy is
given by
1
⟨E⟩ = p2
2m
Because ⟨p⟩ = 0, p2 = σp2 where σp can be called the uncertainty in p. Using the uncer-
tainty principle, show that the energy must be at least as large as ℏ2 /8ma2 because σx , the
uncertainty in x, cannot be larger than a.

19. Show that the normalized wave function for a particle in a three-dimensional box with sides
of length a, b, and c is

8 1/2
 
nx πx ny πy nz πz
ψ(x, y, z) = sin sin sin
abc a b c

4
20. Show that ⟨p⟩ = 0 for the ground state of a particle in a three-dimensional box with sides of
length a, b, and c.

21. What are the degeneracies of the first four energy levels for a particle in a three- dimensional
box with a = b = 1.5c?

22. The quantized energies of a particle in a box result from the boundary conditions, or from
the fact that the particle is restricted to a finite region. In this problem, we investigate the
quantum-mechanical problem of a free particle, one that is not restricted to a finite region.
The potential energy V (x) is equal to zero and the Schrödinger equation is
d2 ψ 2mE
+ 2 ψ(x) = 0 −∞<x<∞
dx2 ℏ
Note that the particle can lie anywhere along the x axis in this problem. Show that the two
solutions of this Schrödinger equation are
1/2 x/ℏ
ψ1 (x) = A1 ei(2mE) = A1 eikx

and
1/2 x/ℏ
ψ2 (x) = A2 e−i(2mE) = A2 e−ikx

where
(2mE)1/2
k=
ℏ
Show that if E is allowed to take on negative values, then the wave functions become un-
bounded for large x . Therefore, we will require that the energy, E, be a positive quantity.
To get a physical interpretation of the states that ψ1 (x) and ψ2 (x) describe, operate on ψ1 (x)
and ψ2 (x) with the momentum operator P̂ , and show that
dψ1
P̂ ψ1 = −iℏ = ℏkψ1
dx
and
dψ2
P̂ ψ2 = −iℏ = −ℏkψ2
dx
Notice that these are eigenvalue equations. Our interpretation of these two equations is that
ψ1 describes a free particle with fixed momentum ℏk and that ψ2 describes a particle with
fixed momentum −ℏk. Thus, ψ1 describes a particle moving to the right and ψ2 describes
a particle moving to the left, both with a fixed momentum. Notice also that there are no
restrictions on k, and so the particle can have any value of momentum. Now show that
ℏ2 k 2
E=
2m
Notice that the energy is not quantized; the energy of the particle can have any positive
value in this case because no boundaries are associated with this problem. Last, show that
ψ1∗ (x)ψ1 (x) = A∗1 A1 = |A1 |2 = constant, and that ψ2 (x)ψ2 (x) = A∗2 A2 = |A|2 = constant.
Discuss this result in terms of the probabilistic interpretation of ψ ∗ ψ. Also discuss the
application of the uncertainty principle to this problem. What are σp and σx ?