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The multiplet splittings of core p-vacancy levels have recently been observed in various transition-metal complexes and in some rare-earth as well as actinide complexes. This paper presents the calculation of the multiplet structure of core p-vacancy levels in the Hartree-Fock free-ion approximation. The spin-orbit and crystal-field effects have been included. The cases studied are Mn^2+ in MnF₂ and the free ion Fe^3+. For 3p vacancies these effects appear to be unimportant from the point of view of photoelectron spectroscopy owing to the limited resolution of the technique. For 2p vacancies the spin-orbit interaction is comparable to the electrostatic interaction between the electrons and both the interactions must be considered simultaneously. The conclusion is that the x-ray photoelectron spectra of inner-core electrons are more suitable for chemical analysis than those of outer electrons which, in addition, contain large correlation and many-body effects.
Gupta et al. (Mon,) studied this question.