An SCF- Xα MO study of core photoemission satellites in gaseous TiI 4, VCl 4, RuO 4 and NiCl 2

Abstract

SCF- Xα MO calculations for TiCl 4, TiI 4, VCl 4, RuO 4 and NiCl 2 indicate that ligand p → metal d orbital excitations will generate metal core photoemission satellites having small intensities (∼5–10% that of the main peak) and low energies (<5eV from the main peak for the halides). The calculated energies and intensities are in reasonable agreement with experiment for TiCl 4 and TiI 4, the only molecules whose satellite spectra have been studied. The high intensity of the higher-energy (>7 eV) satellites observed for the Ti compounds is not reproduced by the present calculations, in which bound empty orbitals of Rydberg character are employed. It is suggested that the final-state orbital in the high-energy satellite case is actually a continuum orbital of “shape-resonance” type which is localized in the interior of the molecule.