Problem Set: Classic Wave Equation

Quantum Chemistry
Feb-Jun, 2024
Marcos Becerra & Manuel Caetano

1 Classic Wave Equation

Taken from Quantum Chemistry by Donald McQuarrie
1. Find the general solutions to the following differential equations
d2 y dy
a) −4 + 3y = 0
dx2 dx
d2 y dy
b) 2 + 6 =0
dx dx
dy
c) + 3y = 0
dx
d2 y dy
d) 2 + 2 −y =0
dx dx
d2 y dy
e) 2 − 3 + 2y = 0
dx dx

2. Solve the following differential equations:

2
d y dy
a) dx 2 − 4y = 0 y(0) = 2 dx (at x = 0) = 4
d2 y dy dy
b) dx2 − 5 dx + 6y = 0 y(0) = −1 dx (at x = 0) = 0
dy
c) dx − 2y = 0 y(0) = 2

3. Prove that x(t) = cos ωt oscillates with a frequency ν = ω/2π. Prove that x(t) = A cos ωt +
B sin ωt oscillates with the same frequency, ω/2π.

4. Solve the following differential equations:

2
a) ddt2x + ω 2 x(t) = 0 x(0) = 0 dx
dt (at t = 0) = ν0
2
b) ddt2x + ω 2 x(t) = 0 x(0) = A dx
dt (at t = 0) = ν0

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 Prove in both cases that x(t) oscillates with frequency ω/2π.

5. The general solution to the differential equation:

d2 x
+ ω 2 x(t) = 0
dt2
is
x(t) = c1 cos(ωt) + c2 sin(ωt)

For convenience, we often write this solution in the equivalent forms:

x(t) = A sin(ωt + ϕ)
or
x(t) = B cos(ωt + ψ)

Show that all three expressions for x(t) are equivalent. Derive equations for A and ϕ in terms
of c1 and c2 , and for B and ψ in terms of c1 and c2 .Show that all three forms of x(t) oscillate
with frequency ω/2π. Hint: Use the trigonometric identities

sin(α + β) = sin α cos β + cos α sin β and cos(α + β) = cos α cos β − sin α sin β

6. In all the differential equations we have discussed so far, the values of the exponents α that
we have found have been either real or purely imaginary. Let us consider a case in which α
turns out to be complex. Consider the equation

d2 y dy
2
+2 + 10y = 0
dx dx
If we substitute y(x) = eαx into this equation, we find that α2 +2α+10 = 0 or that α = −1±3i
The general solution is

y(x) = c1 e(−1+3i)x + c2 e(−1−3i)x

= c1 e−x e3ix + c2 e−x e−3ix

Show that y(x) can be written in the equivalent form

y(x) = e−x (c3 cos 3x + c4 sin 3x)

Thus we see that complex values of the α′ s lead to trigonometric solutions modulated by an
exponential factor. Solve the following equations:
2
d y dy
(a) dx 2 + 2 dx + 2y = 0

2
d y dy
(b) dx 2 − 6 dx + 25y = 0

d2 y dy 2 2 y =0


(c) dx 2 + 2β dx + β + ω

2
d y dy dy
(d) dx 2 + 4 dx + 5y = 0 y(0) = 1 dx (at x = 0) = −3

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 Figure 1: A body of mass m connected to a wall by a spring

7. This problem develops the idea of a classical harmonic oscillator. Consider a mass m attached
to a spring as shown in the following figure. Suppose there is no gravitational force acting
on m, so the only force is from the spring. Let the relaxed or undistorted spring length be
x0 . Hooke’s law says that the force acting on the mass m is f = −k (x − x0 ),where k is a
constant characteristic of the spring and is called the spring’s force constant. Note that the
minus sign indicates the direction of the force: to the left if x > x0 extended) and to the right
if x < x0 (compressed). The momentum of the mass is

dx d(x − x0 )
p=m =m
dt dt
Newton’s second law says that the rate of change of momentum is equal to a force
dp
=f
dt
Replacing f (x) by Hooke’s law, show that

d2 (x − x0 )
m = −k (x − x0 )
dt2
Upon letting ξ = x − x0 be the displacement of the spring from its undistorted length, then

d2 ξ
m + kξ = 0
dt2
Given that the mass starts at ξ = 0 with an initial velocity v0 , show that the displacement is
given by "  #
 m 1/2 k 1/2
ξ(t) = v0 sin t
k m
Interpret and discuss this solution. What does the motion look like? What is the frequency?
What is the amplitude?

8. Modify Problem 7 to the case where the mass moves through a viscous medium with a viscous
force proportional to but opposite the velocity. Show that the equation of motion is

d2 ξ dξ
m 2
+γ + kξ = 0
dt dt
where γ is the viscous drag coefficient. Solve this equation and discuss the behavior of ξ(t)
for various values of m, γ, and k. This system is called a damped harmonic oscillator.

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 9. Consider the linear second-order differential equation
d2 y dy
2
+ a1 (x) + a0 (x)y(x) = 0
dx dx
Note that this equation is linear because y(x) and its derivatives appear only to the first power
, and there are no cross terms. However, it does not have constant coefficients, and there is
no general, simple method for solving it like there is if the coefficients were constants. Each
equation of this type must be treated more or less individually. Nevertheless, because it is
linear, we must have that, if y1 (x) and y2 (x) are any two solutions, then a linear combination,
y(x) = c1 y1 (x) + c2 y2 (x)
where c1 and c2 are constants, is also a solution. Prove that y(x) is a solution.

10. The Schrödinger equation for a particle of mass m that is constrained to move freely along a
line between 0 and a is:
d2 ψ
 2 
8π mE
+ ψ(x) = 0
dx2 h2
with the boundary condition
ψ(0) = ψ(a) = 0
In this equation, E is the energy of the particle and ψ(x) is its wave function. Solve this
differential equation for ψ(x), apply the boundary conditions, and show that the energy can
have only the values
n 2 h2
En = n = 1, 2, 3, . . .
8ma2
or that the energy is quantized.

11. Prove that the number of nodes for a vibrating string clamped at both ends is n − 1 for the
nth harmonic.

12. Prove that  

2π
y(x, t) = A sin (x − vt)
λ
is a wave of wavelength λ and frequency ν = v/λ traveling to the right with a velocity v.

13. Suppose, a particle is constrained to move freely over the surface of a rectangle of sides a and
b. The Schrödinger equation for this problem is
∂2ψ ∂2ψ
 2 
8π mE
+ + ψ(x, y) = 0
∂x2 ∂y 2 h2
with the boundary conditions:
ψ(0, y) = ψ(a, y) = 0 for all y, 0≤y≤b
ψ(x, 0) = ψ(x, b) = 0 for all x, 0≤x≤a
Solve this equation for ψ(x, y), apply the boundary conditions, and show that the energy is
quantized according to:
n2x h2 n2y h2 nx = 1, 2.3 . . .
Enx ny = +
8ma2 8mb2 ny = 1, 2.3 . . .

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14. Extend Problems 10 and 13 to three dimensions, where a particle is constrained to move
freely throughout a rectangular box of sides a, b, and c. The Schrödinger equation for this
system is
d2 ψ d2 ψ d2 ψ
 2 
8π mE
+ 2 + 2 + ψ(x, y, z) = 0
dx2 dy dz h2
and the boundary conditions are that ψ(x, y, z) vanishes over all the surfaces of the box.

15. Show that Equations

Tnm (t) = Enm cos ωnm t + Fnm sin ωnm t (1)

and

Tnm (t) = Gnm cos (ωnm t + ϕnm ) (2)

are equivalent. How are Gnm and ϕnm in Equation 2 related to the quantities in Equation 1?

16. Prove that un (x, t), the nth normal mode of a vibrating string,
nπx
un (x, t) = (Fn cos ωn t + Gn sin ωn t) sin n = 1, 2, . . .
l
can be written as the superposition of two similar traveling waves moving in opposite direc-
tions. Let ϕn = 0 in
∞ ∞
X nπx X
u(x, t) = An cos (ωn t + ϕn ) sin = un (x, t)
l
n=1 n=1
.