Calculation of the satellite structure in the X-ray photoelectron spectra of metal carbonyls

Abstract

Configuration interaction calculations of the satellite peaks associated with carbon 1s ionization of Ni(CO)₄ are described and used to interpret these satellite peaks in transition metal carbonyls. Due to computational constraints, the Ni(CO)₄ basis results in the ground state wavefunction being artifically asymmetric. The observed spectrum is interpreted in terms of states arising from single and double excitations from the highest filled orbital (M3d) to the first virtual orbital (COπ*) of the ion. A recent alternative assignment of the spectrum is discussed.