The electronic properties of ordered, crystalline solids are determined by the distribution of the electronic states with respect to energy and momentum—the electronic band structure of the solid. Theoretical models of photoemission from solids show that this distribution is, for the most part, preserved in the photoelectric effect. The phenomenological three-step model for ultraviolet and soft X-ray excitation decomposes the effect into these steps:
# Inner photoelectric effect in the bulk of the material that is a direct optical transition between an occupied and an unoccupied electronic state. This effect is subject to quantum-mechanical selection rules for dipole transitions. The hole left behind the electron can give rise to secondary electron emission, or the so-called Auger effect, which may be visible even when the primary photoelectron does not leave the material. In molecular solids phonons are excited in this step and may be visible as satellite lines in the final electron energy.
# Electron propagation to the surface in which some electrons may be scattered because of interactions with other constituents of the solid. Electrons that originate deeper in the solid are much more likely to suffer collisions and emerge with altered energy and momentum. Their mean-free path is a universal curve dependent on electron's energy.
# Electron escape through the surface barrier into free-electron-like states of the vacuum. In this step the electron loses energy in the amount of the work function of the surface, and suffers from the momentum loss in the direction perpendicular to the surface. Because the binding energy of electrons in solids is conveniently expressed with respect to the highest occupied state at the Fermi energy , and the difference to the free-space (vacuum) energy is the work function of the surface, the kinetic energy of the electrons emitted from solids is usually written as .
There are cases where the three-step model fails to explain peculiarities of the photoelectron intensity distributions. The more elaborate one-step model treats the effect as a coherent process of photoexcitation into the final state of a finite crystal for which the wave function is free-electron-like outside of the crystal, but has a decaying envelope inside.