I am currently watching a series of lectures on Nuclear Physics. One of the topics covered is the emission and absorption of X-Rays. This got me thinking about some of the physical chemistry I took as an undergraduate, in particular, about the way photons interact with electrons.
My basic photon/electron understanding: Electrons absorb photons that are at energies equivalent to the energy gap between different orbitals. Also, an electron emits a photon at an energy equal to the energy gap of the transition the electron undergoes between orbitals.
My question is what governs the absorption of a photon by an electron when the energy of the photon doesn't correspond to a transition state, ie when the electron is ejected from the material.
NOTE: This is not a duplicate question. Answers to similar questions so far have been about whether or not this type of process is allowed. I am not confused that it is allowed. I am curious to know how one would go about understanding what goes into figuring out which electrons in an atom are more likely to absorb an incoming photon given that it exceeds the work function of the material.