Satellites in X-Ray photoelectron Spectra of Transition-Metal Compounds

Appearance of satellite lines in the X-ray photoelectron emission from the 2 p -shell of the metal ion transition-metal compounds are ascribed to the increase of covalency due to the creation of an inner-core hole. For this argument a simple two-configuration model is used, which reveals a shortcoming once ab initio calculations of the line positions and intensities are attempted. The molecular-orbital calculation of multiplet structure of the satellite is performed by taking into account a change of the atomic d -orbital due to the hole in the molecular cluster of (NiF 6 ) 4- , and a reasonable agreement with experiments is obtained. The reduction of the Coulomb-interaction parameters found in the analysis of the main line can also be explained by our theory. The result shows that the conventional equivalent-core approximation overestimates effects of the hole.