Estimation of Ce 4f–5d Interaction by Analysis of Partial Fluorescence Yield at the Ce L3 Edge of CeO2

Abstract

Partial fluorescence yield (PFY) spectroscopy, which corresponds to a high-resolution version of the X-ray absorption spectroscopy (XAS), is experimentally performed at the Ce L3 edge of CeO2, and the result is theoretically analyzed using an impurity Anderson model (IAM). In order to estimate the Ce 4f–5d interaction Ufd, we employ a semi-empirical IAM framework based on the local density approximation+U method; Slater–Koster parameters describing the valence of CeO2 are estimated by band mapping within the linear combination of atomic orbitals scheme, and the resulting realistic valence structure is considered in the IAM analysis. The global structure of the PFY-XAS result, which consists of the Ce 2p3/2 → 5d dipole transition and the Ce 2p3/2 → 4f quadrupole transition, is excellently reproduced by the calculation. The Ufd value is estimated to be 3.0 eV. We emphasize that the sensitivity of PFY-XAS to Ufd makes it a good ruler for obtaining the Ufd values of Ce compounds.