HERFD-XANES and RIXS study on the electronic structure of trivalent lanthanides across a series of isostructural compounds


HERFD-XANES and RIXS study on the electronic structure of trivalent lanthanides across a series of isostructural compounds

Zasimov, P. V.; Amidani, L.; Retegan, M.; Walter, O.; Caciuffo, R.; Kvashnina, K. O.

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 simulations performed with the density functional theory and atomic multiplet theory computational approaches. The spectral shape and the elemental trends observed in the experimental HERFD-XANES spectra are well reproduced by density functional theory calculations, whilst the pre-edge energy interval is well 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 simulations considering exclusively the atomic configuration. Guided by theoretical predictions, we discuss possible origins of the observed spectral features and the trends in energy splitting across the series. The insight in the electronic structure of trivalent lanthanides compounds demonstrated here and obtained with advanced X-ray spectroscopies coupled with theoretical simulations can be applied to any lanthanide-bearing compound and be of great interest for all research fields involving lanthanides

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Publ.-Id: 32846