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Atomic many-body effects in the 4f XPS of the U5+ and U4+ cations: part II: consequences of orbital relaxation

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Abstract

Ab initio, fully relativistic four component theory was used to determine atomic many-body effects for the 4f X-ray photoelectron spectra (XPS) of U5+ and U4+ cations. Many-body effects were included through the use of configuration interaction (CI) wavefunctions, WF‘s, that allow the mixing of XPS allowed and XPS forbidden configurations. This work extends our earlier study of the U 4f XPS in that the orbitals for the final, ionic states of the cations are allowed to relax in the presence of the 4f core-hole. In the earlier work, orbitals optimized for the initial state were frozen and also used for the final, ionic states. While the main XPS features are similar in both cases, using relaxed orbitals for the ionic states introduces changes in the multiplet splitting and in the 4f5/2 and 4f7/2 spin–orbit splitting. The extent of configuration mixing for the U5+ and U4+ final state WF’s is characterized by the magnitude of the intensity lost by the main peaks to satellites. Overall, the use of relaxed orbitals improves the agreement between the theoretical XPS for the U4+ cation and the experimental measurements for UO2.

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Authors and Affiliations

  1. Department of Chemistry, University of North Texas, Denton, TX, USA

    Paul S. Bagus

  2. Chemical Science Division, Pacific Northwest National Laboratory, Richland, WA, 993, USA

    Eugene S. Ilton

Authors
  1. Paul S. Bagus
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  2. Eugene S. Ilton
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Correspondence to Paul S. Bagus.

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Contribution to the Serafin Fraga Memorial Issue.

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Bagus, P.S., Ilton, E.S. Atomic many-body effects in the 4f XPS of the U5+ and U4+ cations: part II: consequences of orbital relaxation. Theor Chem Account 118, 495–502 (2007). https://doi.org/10.1007/s00214-007-0364-9

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  • DOI: https://doi.org/10.1007/s00214-007-0364-9

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