Lecture 4: Particles in a 2D box, degeneracy,

harmonic oscillator

1 Particle in a 2D Box
In this case, the potential energy is given by
V (x, y) = 0 0 ≤ x ≤ a, 0 ≤ y ≤ b
= ∞ otherwise
The Hamiltonian operator is given by
~2
 2
d2

d
− + + V (x, y)
2m dx2 dy2
and the corresponding Schrödinger equation is given by
~2 d2 ψ(x, y) d2 ψ(x, y)
 
− + = Eψ(x, y)
2m dx2 dy2
inside the box and ψ(x, y) = 0 outside the box.
The wavefunction inside the box can be solved by separation of variables
ψ(x, y) = ψx (x)ψy (y) which can be shown to lead to the equations
~2 d2 ψx (x)
− = Ex ψx (x)
2m dx2
and
~2 d2 ψy (y)
− = Ey ψy (y)
2m dy2
This is simply the product of a two independent Particles in 1-D boxes so we
have r
2 nx πx
ψx (x) = sin( )
a a

1
and r
2 ny πy
ψy (y) = sin( )
b b
where
n2x h2
Enx =
8ma2
and
n2y h2
Eny =
8mb2
The total energy E is now quantized by two numbers, nx and ny and is given
by
h2 n2x n2y
 
Enx,ny = + 2
8m a2 b
The lowest energy state is nx = ny = 1. If a > b, the next lowest energy
state is nx = 2,ny = 1. When a = b, we have a degeneracy Enx,ny = Eny,nx .
We can extend this particle in a box problem to the following situations:

1. Particle in a 3D box - this has many more degeneracies. This is the

classic way of studying density of states in metals or other free-electron
systems.

2. 2 or more noninteracting particles in a box. In this case, we have to

worry as to whether the particles are fermions or bosons and keep track
of Pauli’s exclusion principle if they are fermions. This is particularly
relevant for the modeling of pi-electrons in conjugated alkenes as par-
ticles in a box.

3. Particles in boxes that are shaped differently, particle in a ring (Use of

curvilinear coordinates).

Many of the important principles of quantum mechanics are illustrated by

the various particle-in-a-box systems that we have studied. Quantization,
degeneracies, role of dimensionality, etc. are naturally seen in these systems.
We now move to other quantum systems wherein different aspects of the
problems relating to atomic and molecular structure are seen.

2
2 The 1-D Harmonic Oscillator model
We have considered the particle in a box system which has either V (x) = 0
or V (x) = ∞. We now want to consider a system where V (x) is a quadratic
function of x given by
1
V (x) = kx2
2
The motivation for this choice is the classical harmonic oscillator problem of

U(x)

x
a mass and a spring system shown below where x is the displacement from
the equilibrium position.
Interestingly, this can also be viewed as a 2 particle system interacting
with a spring force. When the equations of motion are converted to center
of mass frame, the relative motion of the two particles follows the harmonic
motion described above. For this reason, this turns out to be an important
starting model for describing vibrations in diatomic molecules.
The Hamiltonian operator for this system is given by
~2 d2 1
H(x) = − + kx2
2m dx 2 2

3
 leq

x
m

The value of x is assumed to vary from −∞ to +∞. This might seem a

little surprising at first since the spring cannot be compressed more than its
equilibrium length. However, we keep in mind that the harmonic motion is
only for small displacements, so there is a separation of length scales. In
other words, we are assuming that x << leq . So the limits are only necessary
to complete the formal calculation.
The corresponding Schrödinger equation is given by

~2 d2 ψ(x) 1 2
− + kx ψ(x) = Eψ(x)
2m dx2 2
This rather simple looking equation turns out to be fairly difficult to solve.
We will not try to derive the solution here, but simply take the solutions and
examine the results.