Abstract
By explicitly taking into account the actual environment, a study of electron relaxation and subsequent radiative and non-radiative de-excitation of a singly or multiply ionised C atom gives a rather complex picture of environmental and multiple-ionisation effects on X-ray fluorescence yields. The pertinent discussion in the literature is commonly treated statistically, according to which any valence-electron depletion, caused either by the chemical surroundings or by primary ionisation would curtail X-ray emission less than Auger transitions, thus inevitably increasing the fluorescence yields. In reality, non-radiative vacancy filling is also determined by the particular manner in which the effective valence-charge fractions are distributed among the valence electrons. The two effects result in opposite variations of fluorescence yields. It is interatomic relaxation that shows which trend is dominant, favouring the latter.

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