2025/05/20 by Sergei M. Butorin, Butorin, Sergei M. · 1 citation
Materials Science · Chemistry · #Nuclear Materials and Properties #Radioactive element chemistry and processing #Nuclear materials and radiation effects
paper · pdf · doi:10.48550/arxiv.2505.14284
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.