High-resolution valence band RIXS at the actinide M$_{4,5}$-edges

Abstract

Understanding the electronic structure of actinide materials is crucial for both fundamental research and nuclear applications. The partially filled 5f shells exhibit complex behavior due to strong correlations and ligand hybridization, requiring advanced spectroscopic techniques. Here, we report on the development and application of high-resolution valence-band resonant inelastic x-ray spectroscopy (VB-RIXS) experiments at the uranium M$_{4,5}$ edges (3551 and 3725\,eV). We present data of UO$_2$, a well-established model actinide compound. VB-RIXS is particularly well suited for probing the 5f-shell electronic structure, as it probes, in contrast to core-to-core RIXS, excitations without leaving a high-energy core hole in the final state. In VB-RIXS, we achieve energy resolutions of 50\,meV (M$_5$) and 90\,meV (M$_4$), enabling the resolution of multiplet excitations and crystal-field effects, as well as charge-transfer and fluorescence-like features with unprecedented clarity. As such, high resolution VB-RIXS offers direct insights into both low-energy, near ground-state properties and high-energy hybridization and covalency effects. Our results demonstrate the power of VB-RIXS as a versatile and powerful tool for probing the strongly correlated electronic structure of actinide materials, providing essential input for quantitative modeling and the validation of theoretical concepts.