Molecular Auger resonance Raman effect: A high resolution study on the resonance Auger decay of HBr after the Br 3<i>d</i>→5<i>p</i>π Rydberg transition

Abstract

High resolution resonance Auger spectra of HBr are recorded with the photon energy tuned to the HBr Br 3d\ensuremath{\rightarrow}5p\ensuremath{\pi} resonance which is broadened by the molecular ligand-field splitting. The spectra show the characteristics of the Auger resonance Raman effect: The resonance Auger peak positions move linearly with the photon energy, and the lifetime broadening does not contribute to the widths of the resonance Auger peaks. Moreover, the ligand-field splitting effects are also absent from the resonance Auger spectra. The prospect for high resolution studies on molecular inner shell decays, using resonance Auger spectroscopy to eliminate both lifetime and ligand-field effects, is discussed.