Electronic-Structure Interpretation: How Much Do We Understand Ce L 3 XANES?

Historically, cerium has been attractive for pharmaceutical and industrial applications. The cerium atom has the unique ability to cycle between two chemical states (Ce(III) and Ce(IV)) and drastically adjust its electronic configuration: [Xe] 4f 1 5d 1 6s 2 in response to a chemical reaction. Understanding how electrons drive chemical reactions is an important topic. The most direct way of probing the chemical and electronic structure of materials is by X-ray absorption spectroscopy (XAS) or X-ray absorption near-edge structure (XANES) in high energy resolution fluorescence detection (HERFD) mode. Such measurements at the Ce L 3 edge have the advantage of a high penetration depth, enabling in-situ reaction studies in a time-resolved manner and investigation of material production or material performance under specific conditions. But how much do we understand Ce L 3 XANES? This article provides an overview of the information that can be extracted from experimental Ce L 3 XAS/XANES/HERFD data. A collection of XANES data recorded on various cerium systems in HERFD mode is presented here together with detailed discussions on data analysis and the current status of spectral interpretation, including electronic structure calculations.