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  • Open Access

Localization versus hybridization of f states in actinide and lanthanide dioxides probed in core-level photoemission spectra

Sergei M. Butorin*

  • Condensed Matter Physics of Energy Materials, X-ray Photon Science, Department of Physics and Astronomy, Uppsala University, P.O. Box 516, SE-751 20 Uppsala, Sweden

  • *Contact author: sergei.butorin@physics.uu.se
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Phys. Rev. B 112, 125118 – Published 9 September, 2025

DOI: https://doi.org/10.1103/8x4b-6651

Abstract

The degrees of the localization and hybridization of the valence f states/covalency of the chemical bonding in actinide and lanthanide dioxides were investigated using the atomic, crystal-field multiplet and Anderson impurity model (AIM) approaches to calculate actinide 5d and lanthanide 3d x-ray photoemission spectra (XPS). The actinide 5d XPS can be largely described within atomic, crystal-field multiplet theory due to an extended multiplet structure as a result of the strong interaction of 5f electrons with a 5d core hole. The multiplet structure was found to be quite sensitive to the oxidation state of actinides. In turn, the lanthanide 3d XPS description requires the AIM type of calculations due to significant 4f–O 2p hybridization effects. As a result derived from the analysis of the XPS spectra, an increase in the f-shell occupancy in the ground state due to the f–O 2p hybridization and covalency of the chemical bonding appears to be higher in lanthanide dioxides as compared to actinide dioxides.

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Phys. Rev. B 112, 125118– Published 9 September, 2025
  • Received 19 May 2025
  • Revised 14 July 2025
  • Accepted 28 August 2025
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Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI. Funded by Bibsam.

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