Characteristics of chemical bonding of pentavalent uranium in La-doped UO2

Abstract

The effect of La doping on the electronic structure of U in UO₂ was studied using an advanced technique, namely, X-ray absorption spectroscopy (XAS) in the high-energy-resolution fluorescence-detection (HERFD) mode, at the U 3d_3/2 (M₄) edge. Thanks to a significant reduction of the core–hole lifetime broadening and distinct chemical shifts of the HERFD-XAS lines, the U(V) formation as a result of La doping was identified. The isolated contribution of U(V) in the M₄ HERFD-XAS spectrum reveals the so-called charge-transfer satellites due to the U 5f–O 2p hybridization. The analysis of the experimental data within the framework of the Anderson impurity model (AIM) indicates a significant change in the characteristics and degree of covalency for the chemical bonding in the U(V) subsystem of UO₂ as compared to undoped UO₂, which is a Mott–Hubbard system. The results are also supported by AIM calculations of X-ray photoelectron and optical absorption data.