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Title: Inner-shell photoionization and core-hole decay of Xe and XeF{sub 2}

Photoionization cross sections and partial ion yields of Xe and XeF{sub 2} from Xe 3d{sub 5/2}, Xe 3d{sub 3/2}, and F 1s subshells in the 660–740 eV range are compared to explore effects of the F ligands. The Xe 3d-ϵf continuum shape resonances dominate the photoionization cross sections of both the atom and molecule, but prominent resonances appear in the XeF{sub 2} cross section due to nominal excitation of Xe 3d and F 1s electrons to the lowest unoccupied molecular orbital (LUMO), a delocalized anti-bonding MO. Comparisons of the ion products from the atom and molecule following Xe 3d photoionization show that the charge-state distribution of Xe ions is shifted to lower charge states in the molecule along with production of energetic F{sup +} and F{sup 2+} ions. This suggests that, in decay of a Xe 3d core hole, charge is redistributed to the F ligands and the system dissociates due to Coulomb repulsion. The ion products from excitation of the F 1s-LUMO resonance are different and show strong increases in the yields of Xe{sup +} and F{sup +} ions. The subshell ionization thresholds, the LUMO resonance energies, and their oscillator strengths are calculated by relativistic coupled-cluster methods and agreemore » well with measurements.« less
Authors:
; ;  [1] ;  [2] ; ;  [3]
  1. X-ray Science Division, Argonne National Laboratory, Argonne, Illinois 60439 (United States)
  2. Synchrotron Radiation Center, University of Wisconsin–Madison, Stoughton, Wisconsin 53589 (United States)
  3. Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, Texas 78712 (United States)
Publication Date:
OSTI Identifier:
22415966
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 22; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CHARGE STATES; COMPARATIVE EVALUATIONS; COULOMB FIELD; CROSS SECTIONS; ELECTRONS; EV RANGE; EXCITATION; HOLES; LIGANDS; MOLECULAR ORBITAL METHOD; MOLECULES; OSCILLATOR STRENGTHS; PHOTOIONIZATION; RESONANCE; XENON FLUORIDES; XENON IONS