3d-4f Resonant Inelastic X-ray Scattering of Actinide Dioxides: Crystal-Field Multiplet Description.

A theoretical overview of the core-to-core (3-4) resonant inelastic X-ray scattering (RIXS) spectra of actinide dioxides AnO (An = Th, U, Np, Pu, Am, Cu, Bk, Cf) is provided. The 3-4 RIXS maps were calculated using crystal-field multiplet theory and turned out to be significantly different at the An vs edges, because of selection rules and final state effects. The results of the calculations allowed for a general analysis of so-called high-energy-resolution fluorescence-detected X-ray absorption (HERFD-XAS) spectra. The cuts of the calculated RIXS maps along the incident energy axis at the constant emitted energy, corresponding to the maximum of the RIXS intensity, represented the HERFD spectra and provided their comparison with calculated conventional X-ray absorption (XAS) spectra with a reduced core-hole lifetime broadening at the An and edges. Although the An HERFD profiles were found to depart from the X-ray absorption cross-section, in terms of appearing additional transitions, the results of calculations for the An edges demonstrate overall better agreement between the HERFD and XAS spectra for most dioxides, keeping in mind a restricted HERFD resolution, because of the core-hole lifetime broadening in the final state. The results confirm the utility of HERFD for the An chemical state determination and indicate the importance of calculating the entire RIXS process in order to interpret the HERFD data correctly.