Probing Multiconfigurational States by Spectroscopy: The Cerium XAS L3 -edge Puzzle.

Abstract

The Ce L3 edge XAS spectra of CeO2 and cerocene [Ce(C8 H8 )2 ] were calculated with relativistic ab-initio multireference wavefunction approaches capable of reproducing the observed spectra accurately. The study aims to resolve the decades-long puzzle regarding the relationship between the number and relative intensities of the XAS peaks and the 4f electron occupation in the ground state (GS) versus the core-excited states (ESs). CeO2 and cerocene exemplify the different roles of covalent bonding and wavefunction configurational composition in the observed intensity patterns. Good agreement is found between the calculated GS 4f-shell occupations and the value derived from XAS measurements using peak areas (nf ). The identity of the two-peaked Ce L3 edge is fully rationalized from the perspective of the relaxed wavefunctions for the GS and core ESs. The states underlying the different peaks differ from each other in a surprisingly simple way that can be associated with 4f1 vs. 4f0 sub-configurations. Furthermore, part of one of the cerocene spectral peaks is associated with 4f2 sub-configurations. The pattern therefore reveals excited states that can be interpreted in terms of Ce IV and III oxidation numbers, as long assumed, with Ce II states additionally appearing in the cerocene spectrum. While this work demonstrates the rough accuracy of the conventional approach to determining nf from Ce L3 -edge XAS, limitations are highlighted in terms of the ultimate accuracy of this approach and the potential of observing new types of excited states. The need to determine the sources of nf by calculations, is stressed.