Relating the 4s{sigma}{sup -1} inner-valence photoelectron spectrum of HBr with the Br 3d{sup -1}5l{lambda} resonant Auger spectra: An approach to the assignments
- Institute for Experimental Physics, Freie Universitaet Berlin, Arnimallee 14, D-14195 Berlin, (Germany)
- Department of Chemistry, The University of Western Ontario, London, Ontario, Canada N6A 5B7 (Canada)
- Department of Physical Sciences, University of Oulu, P.O. Box 3000, 90401 Oulu, (Finland)
The high resolution Br 4s{sigma}{sup -1} photoelectron spectrum of HBr is presented together with the resonant Auger spectra resulting from excitations from the 3d core levels to the low-n Rydberg orbitals 5s{sigma}, 5p{sigma}, and 5p{pi}. The very complex spectra can be broadly assigned using two observations. First, the energy splittings of the 4p{pi}{sup -2}5s and 4p{pi}{sup -2}5p states are very similar to the splittings of the 4p{pi}{sup -2}({sup 1}{sigma}{sup +},{sup 1}{delta}, and {sup 3}{sigma}{sup -}) final states seen previously in the normal Auger spectra. Second, the {sup 2}{sigma}{sup +} states, which are the dominant correlation satellites in the complex 4s{sigma}{sup -1} photoelectron spectrum, are often enhanced in the 5s{sigma} resonance Auger spectra. Electron correlation and spin-orbit interaction in the final states are important to understand all of these spectra. Unlike the normal Auger spectra, vibrational excitations play only a minor role in these spectra, showing that the 5s and 5p Rydberg orbitals have some bonding character.
- OSTI ID:
- 20640179
- Journal Information:
- Physical Review. A, Journal Name: Physical Review. A Journal Issue: 3 Vol. 68; ISSN 1050-2947; ISSN PLRAAN
- Country of Publication:
- United States
- Language:
- English
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