The particle in a box problem is a common application of a quantum
mechanical model to a simplified system consisting of a particle
moving horizontally within an infinitely deep well from which it
cannot escape. The solutions to the problem give possible values of
E and ψ that the particle can possess. E represents allowed energy
values and ψ(x) is a wave function, which when squared gives us the
probability of locating the particle at a certain position within the
box at a given energy level.
The potential energy is 0 inside the box (V=0 for 0<x<a) and goes to
infinity at the walls of the box (V=∞ for x<0 or x>a). We assume the walls
have infinite potential energy to ensure that the particle has zero
probability of being at the walls or outside the box. Doing so significantly
simplifies our later mathematical calculations as we employ
these boundary conditions when solving the Schrödinger Equation.
mass m𝑚 moving in one direction with energy E is
The time-independent Schrödinger equation for a particle of
ℏ is the reduced Planck constant where ℏ=ℎ/2𝜋
m is the mass of the particle
ψ is the stationary time-independent wave function
V(x) is the potential energy as a function of position
E is the energy
This equation can be modified for a particle of mass m𝑚 free to move
parallel to the x-axis with zero potential energy (V = 0 everywhere)
resulting in the quantum mechanical description of free motion in one
dimension:
This equation has been well studied and gives a general solution of:
ψ(x) = Asin(kx) + Bcos(kx)
where A, B, and k are constants.
The solution to the Schrödinger equation we found above is the
general solution for a 1-dimensional system. We now need to apply
our boundary conditions to find the solution to our particular
at 𝑥=0 or 𝑥=a is
system. According to our boundary conditions, the probability of
finding the particle zero. When x=0,
then sin(0)=0 and cos(0)=1; therefore, B must be equal to zero to
fulfill this boundary condition.
ψ(x)=Asin(kx)
We can now solve for our constants ( A and k) systematically to
define the wave function.
Solving for k
Differentiate the wave function with respect to x:
Differentiate the wave function again with respect to x:
Since ψ(x) = Asin(kx), then
If we then solve for k by comparing with the Schrödinger equation
above, we find:
Now we plug k into our wavefunction:
Solving for A
To determine A, we have to apply the boundary conditions again.
Recall that the probability of finding a particle at x = 0 or x = a is
zero. When x=L:
This is only true when
where n = 1,2,3…
Plugging this back in gives us:
To determine A𝐴, recall that the total probability of finding the
particle inside the box is 1, meaning there is no probability of it
being outside the box. When we find the probability and set it equal
to 1, we are normalizing the wavefunction.
For our system, the normalization looks like:
our normalization constant, A:
Which results in the normalized wavefunction for a particle in a 1-
dimensional box:
Step 4: Determine the Allowed Energies
Solving for E results in the allowed energies for a particle in a box:
This is an important result that tells us:
1. The energy of a particle is quantized and
2. The lowest possible energy of a particle is NOT zero. This is called
the zero-point energy and means the particle can never be at
rest because it always has some kinetic energy.
This is also consistent with the Heisenberg Uncertainty Principle: if the
particle had zero energy, we would know where it was in both space and
time.
What does all this mean?
the n=1𝑛=1 and n=2𝑛=2 energy levels look like this:
The wavefunction for a particle in a box at
Exericise 1:
What is the ΔE between the 𝑛=4 and n=5 states for
an F2 molecule trapped within in a one-dimension well of length 3.0 cm?
At what value of n does the energy of the molecule reach ¼kBT¼𝑘𝐵𝑇 at
450 K, and what is the separation between this energy level and the one
immediately above it?
Solution
Since this is a one-dimensional particle in a box problem, the particle has
only kinetic energy (V = 0), so the permitted energies are:
