Atomic Autoionization Observed in nd → O* Molecular Resonances
The excitation of a core electron into an antibonding empty valence orbital of a molecule leads to a quite intense resonance compared to Rydberg transitions in the photoabsorption spectrum. We show the direct experimental evidence of its repulsive character by photoelectron spectroscopy in the case of a d-shell excitation of halogen compounds such as HBr, CH3 Br, HI and CH3 I. The first step of the resonance decay is a very fast dissociation process followed by autoionization of the core excited fragment as a second step. Competition with usual molecular autoionization is found when the mass of the radical linked to the excited atom is increased.
KeywordsPhoton Energy Rydberg State Giant Resonance Electronic Relaxation Electron Energy Loss Spectrum
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