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X-ray Absorption and Resonant Auger Spectroscopy of O2 in the Vicinity of the O 1s_σ* Resonance: Experiment and Theory
Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Materials Science, Soft X-Ray Physics.
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2008 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 128, no 6, 064304- p.Article in journal (Refereed) Published
Abstract [en]

We report on an experimental and theoretical investigation of x-ray absorption and resonant Auger electron spectra of gas phase O-2 recorded in the vicinity of the O 1s ->sigma* excitation region. Our investigation shows that core excitation takes place in a region with multiple crossings of potential energy curves of the excited states. We find a complete breakdown of the diabatic picture for this part of the x-ray absorption spectrum, which allows us to assign an hitherto unexplained fine structure in this spectral region. The experimental Auger data reveal an extended vibrational progression, for the outermost singly ionized X (2)Pi(g) final state, which exhibits strong changes in spectral shape within a short range of photon energy detuning (0 eV>Omega>-0.7 eV). To explain the experimental resonant Auger electron spectra, we use a mixed adiabatic/diabatic picture selecting crossing points according to the strength of the electronic coupling. Reasonable agreement is found between experiment and theory even though the nonadiabatic couplings are neglected. The resonant Auger electron scattering, which is essentially due to decay from dissociative core-excited states, is accompanied by strong lifetime-vibrational and intermediate electronic state interferences as well as an interference with the direct photoionization channel. The overall agreement between the experimental Auger spectra and the calculated spectra supports the mixed diabatic/adiabatic picture.

Place, publisher, year, edition, pages
2008. Vol. 128, no 6, 064304- p.
National Category
Physical Sciences
Research subject
Physics
Identifiers
URN: urn:nbn:se:uu:diva-103174DOI: 10.1063/1.2831920ISI: 000253238200017OAI: oai:DiVA.org:uu-103174DiVA: diva2:217641
Available from: 2009-05-15 Created: 2009-05-15 Last updated: 2017-12-13Bibliographically approved

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