In the X-ray regime, the photoelectric effect in crystalline material is often decomposed into three steps:
 1)Inner photoelectric effect . The hole left behind can give rise to auger effect, which is visible even when the electron does not leave the material. In molecular solids phonons are excited in this step and may be visible as lines in the final electron energy. The inner photoeffect has to be dipole allowed. The transition rules for atoms translate via the tight-binding model onto the crystal. They are similar in geometry to plasma oscillations in that they have to be transversal.
 2)Ballistic transport of half of the electrons to the surface. Some electrons are scattered.
 3)Electrons escape from the material at the surface.

In the three-step model, an electron can take multiple paths through these three steps. All paths can interfere in the sense of the path integral formulation. For surface states and molecules the three-step model does still make some sense as even most atoms have multiple electrons which can scatter the one electron leaving.

FOR more information read the book:Hügner, S. (2003). Photoelectron Spectroscopy: Principles and Applications. Springer. ISBN 3-540-41802-4.

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