Determination of Uranium Central-Field Covalency with 3d4f Resonant Inelastic X-ray Scattering.
J Am Chem Soc
; 146(32): 22570-22582, 2024 Aug 14.
Article
en En
| MEDLINE
| ID: mdl-39083620
ABSTRACT
Understanding the nature of metal-ligand bonding is a major challenge in actinide chemistry. We present a new experimental strategy for addressing this challenge using actinide 3d4f resonant inelastic X-ray scattering (RIXS). Through a systematic study of uranium(IV) halide complexes, [UX6]2-, where X = F, Cl, or Br, we identify RIXS spectral satellites with relative energies and intensities that relate to the extent of uranium-ligand bond covalency. By analyzing the spectra in combination with ligand field density functional theory we find that the sensitivity of the satellites to the nature of metal-ligand bonding is due to the reduction of 5f interelectron repulsion and 4f-5f spin-exchange, caused by metal-ligand orbital mixing and the degree of 5f radial expansion, known as central-field covalency. Thus, this study furthers electronic structure quantification that can be obtained from 3d4f RIXS, demonstrating it as a technique for estimating actinide-ligand covalency.
Texto completo:
1
Base de datos:
MEDLINE
Idioma:
En
Revista:
J Am Chem Soc
/
Journal of the american chemical society
/
J. am. chem. soc
Año:
2024
Tipo del documento:
Article