Article Dans Une Revue Inorganic Chemistry Année : 2025

Core-Excited States of Linear and Bent Uranyl Complexes: Insights from High-Energy Resolution X-ray Spectroscopy and Relativistic Quantum Chemistry

Résumé

Advanced X-ray spectroscopic techniques are widely recognized as state-of-the-art tools for probing the electronic structure, bonding, and chemical environments of the heaviest elements in the periodic table. In this study, we employ X-ray absorption near-edge structure measurements in high-energy resolution fluorescence detection (HERFD-XANES) mode to investigate the core states arising from excitations out of the U 3d3/2 (M4 edge) levels for molecular complexes in which the uranyl moiety deviates from linearity to varying degrees, and in particular systems containing the UO2Cl2 group such as UO2Cl2·n(H2O) and UO2Cl2(phen)2, which in the latter case exhibits a pronounced O–U–O bending angle. These U M4-edge HERFD-XANES spectra are compared with those of other uranyl complexes reported in the literature. This evaluation is complemented by ab initio relativistic quantum chemistry simulations on the [UO2(NO3)2·n(H2O)], UO2Cl2·n(H2O), and UO2Cl2(phen)2 systems, using two-component time-dependent density functional theory (TD-DFT) with the CAM-B3LYP functional, employing the Tamm-Dancoff approximation (2c-TDA). Our 2c-TDA simulations show modest deviations from the HERFD-XANES data, with peak splittings differing by less than 1 eV from experimental values. These core-excited states were further characterized by natural transition orbital (NTO) analysis. Overall, our results highlight the influence of equatorial ligands on the spectroscopic signatures, particularly pronounced in UO2Cl2(phen)2, where the U 3d3/2 → 5fσu* satellite transition appears at lower energies compared to the other systems studied.

Dates et versions

hal-05027528 , version 1 (09-04-2025)

Identifiants

Citer

Wilken Aldair Misael, Lucia Amidani, Juliane März, Elena F. Bazarkina, Kristina O. Kvashnina, et al.. Core-Excited States of Linear and Bent Uranyl Complexes: Insights from High-Energy Resolution X-ray Spectroscopy and Relativistic Quantum Chemistry. Inorganic Chemistry, 2025, 64 (45), pp.22487-22502. ⟨10.1021/acs.inorgchem.5c04245⟩. ⟨hal-05027528⟩
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