Quantifying the U 5f covalence and degree of localization in U intermetallics

Abstract

A procedure for quantifying the U 5f electronic covalency and degree of localization in U intermetallic compounds is presented. To this end, bulk sensitive hard and soft x-ray photoelectron spectroscopy were utilized in combination with density-functional theory (DFT) plus dynamical mean-field theory (DMFT) calculations. The energy dependence of the photoionization cross sections allows the disentanglement of the U 5f contribution to the valence band from the various other atomic subshells so the computational parameters in the DFT+DMFT can be reliably determined. Applying this method to UGa_{2} and UB_{2} as model compounds from opposite ends of the (de)localization range, we have achieved excellent simulations of the valence band and core-level spectra. The width in the distribution of atomic U 5f configurations contributing to the ground state, as obtained from the calculations, quantifies the correlated nature and degree of localization of the U 5f. The findings permit answering the longstanding question why different spectroscopic techniques give seemingly different numbers for the U 5f valence in intermetallic U compounds.