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

TL;DR

This study investigates the localization and hybridization of $f$ states in actinide and lanthanide dioxides using photoemission spectra and theoretical models, revealing differences in covalency and electronic structure.

Contribution

It combines atomic, crystal-field multiplet, and Anderson impurity models to analyze core-level photoemission spectra, providing new insights into $f$-electron behavior in these materials.

Findings

Actinide $5d$ XPS is well described by multiplet theory.

Lanthanide $3d$ XPS requires Anderson impurity model due to hybridization.

Lanthanide dioxides show higher $f$-shell occupancy and covalency.

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.