Interatomic and Intra-Atomic Configuration Interactions in Core-Level X-Ray Photoemission Spectra of Late Transition-Metal Compounds

We theoretically investigate X-ray photoemission spectra (XPS) from transition metal 2 p and 3 s core levels in late transition metal compounds in terms of an MX 6 cluster model (M=Mn∼Ni; X=halogen or oxygen), paying particular attention to the interplay between the intra-atomic multiplet coupling and covalency mixing effects. In the analysis of 3 s -XPS, we also take into account the intra-atomic configuration interaction between 3 s 1 3 p 6 3 d n and 3 s 2 3 p 4 3 d n +1 electron configurations. The systematic change of 2 p -XPS and 3 s -XPS on going from Ni to Mn compounds or from fluorides to bromides is mainly ascribed to that of the charge transfer energy from X to M ion. In the analysis, we show that the final state effects are very important in the 3 s -XPS as well as in the 2 p -XPS.