Multiplet splitting of manganese core p-levels in MnF2

Abstract

High-resolution X-ray emission spectroscopy (XES) is used to measure splittings of core p-hole final states of Mn²⁺ ions in MnF₂. It turns out that the Hartree-Fock free-ion approximation, including spin-orbit and crystal-field effects, is inadequate for a proper interpretation of the Mn K alpha _1,2 and K beta ₁ structures. A comparison is made with the corresponding core p-level X-ray photoemission spectra (XPS). The observed 2p XES multiplet splitting is absent in the XPS in spite of narrower linewidths obtained by XPS. The K alpha ₁ and K alpha ₂ lines in MnF₂ are broadened by 1.35 and 0.97 eV, respectively, while at least a 1.3 eV broadening of both 2p XPS levels is reported. The discrepancies between the XES and XPS may indicate importance of non-lifetime contributions to intrinsic XPS linewidths in MnF₂.