Sensitivity of x-ray absorption at $5d$ edges of high-valent light actinides to crystal-field strength and covalency effects

The $5f$ states were probed in ThO₂ and U(VI) and U(V) oxides using x-ray absorption spectroscopy at the actinide O4,5 edges. Measured data were analyzed by several approaches including atomic, crystal-field theory and the Anderson impurity model to take into account the hybridization of actinide valence states with oxygen $2p$ states. For Th(IV), the $5f$ states are mainly affected by the crystal-field interaction with the closest neighbors as can be seen from the corresponding spectrum of ThO₂. In turn, for U(VI) and U(V) oxides, the U $5f$-O $2p$ hybridization and high degree of covalency in the chemical bonding play a decisive role increasing the $5f$ occupancy and consequently governing the ground and excited state properties. That is additionally illustrated by results from the calculations of the U $5d$ x-ray photoemission spectra for U(V) in the lattice of La-doped UO₂.