HERFD-XANES and RIXS Study on the Electronic Structure of Trivalent Lanthanides across a Series of Isostructural...

We performed a systematic study of the complexes of trivalent lanthanide cations with the hydridotris(1-pyrazolyl)borato (Tp) ligand (LnTp₃; Ln = La, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, and Lu) using both high-energy-resolution fluorescence-detected X-ray absorption near-edge structure (HERFD-XANES) and resonant inelastic X-ray scattering (RIXS) at the lanthanide L₃ absorption edge. Here, we report the results obtained and we discuss them against calculations performed using density functional theory (DFT) and atomic multiplet theory. The spectral shape and the elemental trends observed in the experimental HERFD-XANES spectra are well reproduced by DFT calculations, while the pre-edge energy interval is better described by atomic multiplet theory. The RIXS data show a generally rather complex pattern that originates from the intra-atomic electron-electron interactions in the intermediate and final states, as demonstrated by the good agreement obtained with calculations using an atomic-only model of the absorber. Guided by theoretical predictions, we discuss the possible origins of the observed spectral features and the trends in energy splitting across the series. The insight into the electronic structure of trivalent lanthanide compounds demonstrated here and obtained with advanced X-ray spectroscopies coupled with theoretical calculations can be applied to any lanthanide-bearing compound and be of great interest for all research fields involving lanthanides.