Hybridization effect on the x-ray absorption spectra for actinide materials: Application to PuB4

Abstract

Studying the local moment and 5$f$-electron occupations sheds insight into the electronic behavior in actinide materials. X-ray absorption spectroscopy (XAS) has been a powerful tool to reveal the valence electronic structure when assisted with theoretical calculations. However, the analysis currently taken in the community on the branching ratio of the XAS spectra generally does not account for the hybridization effects between local $f$-orbitals and conduction states. In this paper, we discuss an approach which employs the DFT+Gutzwiller rotationally-invariant slave boson (DFT+GRISB) method to obtain a local Hamiltonian for the single-impurity Anderson model (SIAM), and calculates the XAS spectra by the exact diagonalization (ED) method. A customized numerical routine was implemented for the ED XAS part of the calculation. By applying this technique to the recently discovered 5$f$-electron topological Kondo insulator PuB$_4$, we determined the signature of 5$f$-electronic correlation effects in the theoretical X-ray spectra. We found that the Pu 5$f$-6$d$ hybridization effect provides an extra channel to mix the $j=5/2$ and $7/2$ orbitals in the 5$f$ valence. As a consequence, the resulting electron occupation number and spin-orbit coupling strength deviate from the intermediate coupling regime.