Photoionization from the Xe 4d orbitals of XeF2

Forbes, R.; Hockett, P.; Powis, I.; Bozek, J. D.; Holland, D. M.P.; Pratt, S. T.

Abstract

We present a comparison of the photoionization dynamics of the 4d shell of XeF2 from threshold to 250 eV to those of the prototypical 4d shell of atomic Xe. The new experimental data include spin-orbit and ligand-field-resolved partial cross sections, photoelectron angular distributions, branching fractions, and lifetime widths for the 4d-hole states. The spin-orbit branching fractions and angular distributions are remarkably similar to the corresponding distributions from atomic Xe across a broad energy interval that includes both the intense shape resonance in the f continuum and a Cooper minimum in the same channel. The angular distributions and branching fractions are also in reasonably good agreement with our first-principles theoretical calculations on XeF2. Data are also presented on the lifetime widths of the substate-resolved 4d-hole states of XeF2. While the trends in the widths are similar to those in the earlier experimental and theoretical work, the linewidths are considerably smaller than in the previous measurements, which may require some reinterpretation of the decay mechanism. Finally, we present new data and an analysis of the Auger electron spectra for ionization above the 4d thresholds and resonant Auger spectra for several pre-edge features.

• Journal Article Type: Article
• Acceptance Date: Oct 26, 2021
• Online Publication Date: Nov 18, 2021
• Publication Date: Nov 21, 2021
• Deposit Date: Nov 18, 2021
• Publicly Available Date: Nov 23, 2021
• Journal: Journal of Chemical Physics
• Print ISSN: 0021-9606
• Electronic ISSN: 1089-7690
• Publisher: AIP Publishing
• Peer Reviewed: Peer Reviewed
• Volume: 155
• Issue: 19
• Article Number: 194301
• DOI: https://doi.org/10.1063/5.0068530
• Keywords: Physical and Theoretical Chemistry; General Physics and Astronomy
• Public URL: https://nottingham-repository.worktribe.com/output/6730211
• Publisher URL: https://aip.scitation.org/doi/10.1063/5.0068530
• Additional Information: This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in R. Forbes, P. Hockett, I. Powis, J. D. Bozek, D. M. P. Holland, and S. T. Pratt , "Photoionization from the Xe 4d orbitals of XeF2", J. Chem. Phys. 155, 194301 (2021) and may be found at https://doi.org/10.1063/5.0068530