AcademyQuantum Wave Functions

Academy

Particle in a Box

Level 1 - Physics topic page in Quantum Wave Functions.

Principle

Hard-wall boundary conditions force standing waves, so a confined particle has discrete energies.

Notation

\(L\)
box width
\(\mathrm{m}\)
\(n\)
positive integer quantum number
1
\(k_n\)
allowed wave number
\(\mathrm{m^{-1}}\)
\(\lambda_n\)
allowed de Broglie wavelength
\(\mathrm{m}\)
\(\psi_n\)
nth normalized spatial eigenfunction
m^{-1/2}
\(E_n\)
nth energy eigenvalue
\(\mathrm{J}\)

Method

Derivation 1: Boundary conditions

For an infinite square well, the wave function must vanish at both walls.

General sinusoidal form
\[\psi(x)=A\sin kx+B\cos kx\]
Left wall
\[\psi(0)=0\Rightarrow B=0\]
Right wall
\[\psi(L)=0\Rightarrow \sin(kL)=0\]

Derivation 2: Quantization

The right-wall condition selects only integer half-wavelengths.

Allowed wave number
\[k_n=\frac{n\pi}{L}\]
Allowed wavelength
\[\lambda_n=\frac{2L}{n}\]

Derivation 3: Energy levels

Kinetic energy is set by the allowed momentum magnitude.

Momentum magnitude
\[p_n=\hbar k_n\]
Energy
\[E_n=\frac{p_n^2}{2m}=\frac{n^2\pi^2\hbar^2}{2mL^2}\]

Rules

For a particle in an infinite well from \(0\) to \(L\):

Eigenfunctions
\[\psi_n(x)=\sqrt{\frac{2}{L}}\sin\left(\frac{n\pi x}{L}\right)\]
Energy levels
\[E_n=\frac{n^2\pi^2\hbar^2}{2mL^2}\]
Center expectation
\[\langle x\rangle=\frac{L}{2}\]

Examples

Question
What is the ratio
\[E_3/E_1\]
for an infinite square well?
Answer
Because
\[E_n\propto n^2\]
\[E_3/E_1=9\]

Checks

  • The quantum number starts at \(n=1\), not \(n=0\).
  • The ground-state energy is nonzero because confinement forces curvature.
  • Larger boxes have more closely spaced energy levels.
  • The probability density is symmetric about the center for every stationary state.