Labeling interacting configurations through an analysis of excitation dynamics in a resonant photoemission experiment: the case of rutile TiO2

A detailed study of resonant photoemission at Ti L2,3 edges of insulating rutile TiO2−x thin film is presented. Pure TiO2 resonating structures, defect-related resonances, resonant Raman-Auger and normal LVV Auger emissions are tracked, including an unpredicted two-hole correlated satellite below the non-bonding part of the valence band. The analysis of excitation dynamics unambiguously addresses the origin of these features and, in particular, the extent of charge transfer effects on the Ti-O bonding in the valence band of rutile, disclosing further applications to the more general case of, formally, d0 oxides.