Determination of Uranium Central-Field Covalency with 3 d 4 f Resonant Inelastic X-ray Scattering.

Autor: Burrow TG; Department of Chemistry, The University of Manchester, Manchester, M13 9PL, U.K.; The University of Manchester at Harwell, Diamond Light Source, Harwell Campus, OX11 0DE, U.K.; Centre for Radiochemistry Research, The University of Manchester, Oxford Road, Manchester, M13 9PL, U.K., Alcock NM; Department of Chemistry, The University of Manchester, Manchester, M13 9PL, U.K.; The University of Manchester at Harwell, Diamond Light Source, Harwell Campus, OX11 0DE, U.K.; Centre for Radiochemistry Research, The University of Manchester, Oxford Road, Manchester, M13 9PL, U.K., Huzan MS; Department of Chemistry, The University of Manchester, Manchester, M13 9PL, U.K.; The University of Manchester at Harwell, Diamond Light Source, Harwell Campus, OX11 0DE, U.K.; Centre for Radiochemistry Research, The University of Manchester, Oxford Road, Manchester, M13 9PL, U.K., Dunstan MA; Department of Chemistry, Technical University of Denmark, 2800 Kongens Lyngby, Denmark., Seed JA; Department of Chemistry, The University of Manchester, Manchester, M13 9PL, U.K.; Centre for Radiochemistry Research, The University of Manchester, Oxford Road, Manchester, M13 9PL, U.K., Detlefs B; European Synchrotron Radiation Facility, 38000 Grenoble, France., Glatzel P; European Synchrotron Radiation Facility, 38000 Grenoble, France., Hunault MOJY; Synchrotron SOLEIL, LOrme des Merisiers, 91190 Saint-Auban, France., Bendix J; Department of Chemistry, University of Copenhagen, 1172 Copenhagen, Denmark., Pedersen KS; Department of Chemistry, Technical University of Denmark, 2800 Kongens Lyngby, Denmark., Baker ML; Department of Chemistry, The University of Manchester, Manchester, M13 9PL, U.K.; The University of Manchester at Harwell, Diamond Light Source, Harwell Campus, OX11 0DE, U.K.; Centre for Radiochemistry Research, The University of Manchester, Oxford Road, Manchester, M13 9PL, U.K.
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2024 Aug 14; Vol. 146 (32), pp. 22570-22582. Date of Electronic Publication: 2024 Jul 31.
DOI: 10.1021/jacs.4c06869
Abstrakt: 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 3 d 4 f resonant inelastic X-ray scattering (RIXS). Through a systematic study of uranium(IV) halide complexes, [UX 6 ] 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 5 f interelectron repulsion and 4 f -5 f spin-exchange, caused by metal-ligand orbital mixing and the degree of 5 f radial expansion, known as central-field covalency. Thus, this study furthers electronic structure quantification that can be obtained from 3 d 4 f RIXS, demonstrating it as a technique for estimating actinide-ligand covalency.
Databáze: MEDLINE
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