Abstract
Free ion relativistic Hartree-Fock results have been used to calculate energies and chemical shifts of K and L X-rays in Mo, Sn and some rare earths. Agreement with experimental chemical shifts in Sm and Eu is good. When exchange is treated fully, the relative magnitude of the Kbeta 1 and Kbeta 3 shifts between di- and tri-valent rare earth ions is shown to depend strongly on whether the electron involved in the change of valence state is from the 4f- or 4f+ group. Further experimental checks on this prediction are suggested. The method is compared with Mossbauer isomer shifts as a means of deducing the electron configuration of crystal chemical bonds.

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