AcademyAtomic Quantum Structure

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Three-Dimensional Schrodinger Equation

Level 1 - Physics topic page in Atomic Quantum Structure.

Principle

The three-dimensional Schrodinger equation applies the same energy-operator idea as the one-dimensional equation, but the kinetic-energy operator uses the full spatial curvature of the wave function.

For a time-independent potential, stationary states solve an eigenvalue equation for allowed energies and spatial wave functions.

Notation

\(\psi(\vec r,t)\)
time-dependent wave function
m^{-3/2}
\(\phi(\vec r)\)
stationary-state spatial wave function
m^{-3/2}
\(U(\vec r)\)
potential energy
\(\mathrm{J}\)
\(\nabla^2\)
three-dimensional Laplacian
\(\mathrm{m^{-2}}\)
\(\hat H\)
Hamiltonian operator
\(\mathrm{J}\)
\(E\)
energy eigenvalue
\(\mathrm{J}\)

Method

Derivation 1: Build the Hamiltonian

In three dimensions, the kinetic-energy operator uses the Laplacian.

Classical energy
\[E=\frac{p_x^2+p_y^2+p_z^2}{2m}+U(\vec r)\]
Laplacian
\[\nabla^2=\frac{\partial^2}{\partial x^2}+\frac{\partial^2}{\partial y^2}+\frac{\partial^2}{\partial z^2}\]
Hamiltonian
\[\hat H=-\frac{\hbar^2}{2m}\nabla^2+U(\vec r)\]

Derivation 2: Separate stationary states

If the potential is not time dependent, energy eigenstates separate into a spatial wave function and a phase factor.

Separated state
\[\psi(\vec r,t)=\phi(\vec r)e^{-iEt/\hbar}\]
Time-independent equation
\[-\frac{\hbar^2}{2m}\nabla^2\phi+U\phi=E\phi\]

Derivation 3: Normalize probability

Probability density is integrated over volume, not just along a line.

Probability density
\[\rho(\vec r)=|\psi(\vec r,t)|^2\]
Normalization
\[\int |\psi(\vec r,t)|^2\,dV=1\]

Rules

Three-dimensional TDSE
\[i\hbar\frac{\partial\psi}{\partial t}=\left[-\frac{\hbar^2}{2m}\nabla^2+U(\vec r)\right]\psi\]
Three-dimensional TISE
\[-\frac{\hbar^2}{2m}\nabla^2\phi+U(\vec r)\phi=E\phi\]
Laplacian
\[\nabla^2=\frac{\partial^2}{\partial x^2}+\frac{\partial^2}{\partial y^2}+\frac{\partial^2}{\partial z^2}\]
Normalization
\[\int|\psi|^2\,dV=1\]

Examples

Question
A free particle has
\[\phi=e^{i\vec k\cdot\vec r}\]
What does
\[\nabla^2\phi\]
equal?
Answer
\[\nabla^2\phi=-k^2\phi\]
so
\[E=\frac{\hbar^2k^2}{2m}\]

Checks

  • The Laplacian replaces the one-dimensional second derivative.
  • Normalization uses a volume integral.
  • Energy eigenvalues come from boundary conditions and normalizability.
  • A stationary state's probability density can be time independent even though its phase changes.