The Quantum Harmonic Oscillator

C. David Sherrill
School of Chemistry and Biochemistry
Georgia Institute of Technology
February 2002
1 Introduction
The harmonic oscillator is extremely useful in chemistry as a model for the vibrational motion
in a diatomic molecule. Polyatomic molecules can be modeled by coupled harmonic oscillators.
The atoms are viewed as point masses which are connected by bonds which act (approximately)
like springs obeying Hookes law. In these notes we will review the classical harmonic oscillator
problem and then discuss the quantum harmonic oscillator.
2 Classical Harmonic Oscillator
Consider two masses m
1
and m
2
at positions x
1
and x
2
, connnected by a spring with spring
constant k. If the rest length of the spring is l
0
, then the two equations governing the motion of
the masses are
m
1
x
1
= k(x
2
x
1
l
0
) (1)
m
2
x
2
= k(x
2
x
1
l
0
). (2)
It will be more convenient to work in terms of (x
2
x
1
l
0
), which is the amount by which the
spring is stretched or compressed from its natural length. Denoting this quantity simply as x, the
equations reduce to
m
1
x
1
= kx (3)
m
2
x
2
= kx. (4)
Subtracting the second equation from the rst gives
m
1
x
1
+ m
2
x
2
= 0. (5)
It will be convenient to introduce the total mass and center of mass coordinates, dened as
M = m
1
+ m
2
(6)
x
cm
=
m
1
x
1
+ m
2
x
2
m
1
+ m
2
, (7)
1
so that we now have
M x
cm
= 0. (8)
This means that the center of mass is not accelerating or decelerating, but is either at rest or
moves with constant velocity; of course this simply reects the fact that there is no external force
acting on the two masses.
Now dividing (3) by m
1
and (4) by m
2
and subtracting the second equation from the rst, we
can obtain
x
1
x
2
= kx

1
m
1
+
1
m
2

. (9)
Since x = x
2
x
1
l
0
, we have x = x
2
x
1
. If we also introduce the reduced mass
=
m
1
m
2
m
1
+ m
2
, (10)
we obtain
x =
k

x, (11)
which is a second-order dierential equation describing the displacement x from the rest length l
0
as a function of time. This can be solved to yield
x(t) = Acos(t) + Bsin(t), (12)
where is dened as
=

(13)
and represents the frequency of oscillation (in rad s
1
) of the oscillator. One could also dene a
frequency in Hertz (s
1
) through = 2.
3 Quantum Harmonic Oscillator
The quantum mechanical version of this harmonic oscillator problem may be written as

h
2
2
d
2
dx
2
+
1
2
kx
2

(x) = E(x). (14)

2
By considering the limiting behavior as x and as x 0, one nds that only certain energies
E
n
yield reasonable solutions (x). The eigenvalues and associated eigenvectors are
E
n
= h

n +
1
2

= h

n +
1
2

, (15)

n
(x) =

h2
2n
(n!)
2

1/4
exp

x
2
2 h

H
n

1/2
x

, (16)
where H
n
are the Hermite polynomials of order n. The Hermite polynomials have a number of
useful properties such as
d
dx
H
n
(x) = 2nH
n1
(x) (17)
H
n+1
(x) = 2xH
n
(x) 2nH
n1
(x) (18)

H
n
(x)H
m
(x)e
x
2
dx =
nm

2
n
n!. (19)
3.1 Units
Absorption or emission of infrared light can cause transitions between energy levels in the harmonic
oscillator. Usually, only transitions between adjacent energy levels (n = 1) occurs with a large
intensity. The frequency of the photon
photon
thus needs to match
h
photon
= E = h. (20)
In this particular case, the frequency of the photon
photon
must be the same as the frequency
of the oscillator. Often,
photon
is measured in wavenumbers (cm
1
) instead of Hertz. Since the
photon obeys c = , the reciprocal wavelength of the photon 1/ can be written as
1

=

c
=

2c
=
1
2c

. (21)
Note that units of cm
1
will result for 1/ if, for example, c is in cm s
1
, k is in J m
2
, and
is in kg. Because of the numerical equivalence between
photon
and , one also frequently
reports in units of cm
1
using the above conversion. Unfortunately, spectroscopists frequently
denote this as , which as we have seen is dened dierently above ( and dier by a
factor of 2). When is reported in cm
1
, this is actually in cm
1
, not the dened above.
One reason for this unfortunate discrepancy in notation is that spectroscopists prefer to use
to refer to fundamental (actually observed) frequencies, which dier from the harmonic (model)
frequencies because the potential wells in diatomic molecules are not strictly harmonic but contain
an anharmonic contribution.
3
What are the units of k? The SI units would be J m
2
, but these are not really natural units
for the very small energies and distances involved in a quantum oscillator. Frequently, these are
reported in mdyn

A
1
. The conversion is
mdyn

A
=
10
8
N
10
10
m

m
m
= 10
2
J
m
2
. (22)
4