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Chemistry 352

Particle in a Box

Particle in a 1D Box via the de Broglie Wavelength

A short, wave-based derivation of energy quantization for an infinite square well.

Consider a particle confined to a one-dimensional region of length L with infinitely high walls at x = 0 and x = L. The particle cannot exist outside the box, so its wave must be zero at the walls: ψ(0) = 0 and ψ(L) = 0.

Using de Broglie relation, a particle with momentum p has wavelength λ = h/p. Inside the box the wave behaves like a standing wave, because reflections from the walls superpose the traveling waves. The boundary conditions force an integer number of half-wavelengths to fit exactly into the length L:

L = nλ/2,   n = 1, 2, 3, …

Therefore the allowed wavelengths are λn = 2L/n. Substituting into de Broglie relation gives quantized momentum:

pn = h/λn = nh/(2L).

For a nonrelativistic particle, the kinetic energy is E = p2/(2m). Hence the allowed energies are

En = pn2/(2m) = (n2h2)/(8mL2),   n = 1, 2, 3, …

This is the key result: confinement plus the standing-wave condition produces discrete wavelengths, which implies discrete momenta and therefore discrete energy levels.

Now it's your turn!

Example 1
Consider a particle in a box of length L = 10 nm. What is the wavelength of the wave function i the n=1 level?
2 nm 5 nm 10 nm 20 nm 40 nm
Example 2
Consider a particle in a box of length L. What is the energy of a particle in the n=2 level?
h2/8mL2 h2/4mL2 h2/2mL2 5h2/8mL2 9h2/8mL2
Example 3
In which system is the momentum of the particle the largest?
n = 1, L = 4 nm n = 2, L = 8 nm n = 2, L = 2 nm

Key points (one glance)