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Autor principal: Butorin, Sergei M.
Formato: Preprint
Publicado: 2025
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Acceso en línea:https://arxiv.org/abs/2505.14284
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author Butorin, Sergei M.
author_facet Butorin, Sergei M.
contents 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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spellingShingle Localization versus hybridization of $f$ states in actinide and lanthanide dioxides probed in core-level photoemission spectra
Butorin, Sergei M.
Strongly Correlated Electrons
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.
title Localization versus hybridization of $f$ states in actinide and lanthanide dioxides probed in core-level photoemission spectra
topic Strongly Correlated Electrons
url https://arxiv.org/abs/2505.14284