Determination of Uranium Central-Field Covalency with 3d4f Resonant Inelastic X-ray Scattering
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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.
| Original language | English |
|---|---|
| Journal | Journal of the American Chemical Society |
| Volume | 146 |
| Issue number | 32 |
| Pages (from-to) | 22570–22582 |
| Number of pages | 13 |
| ISSN | 0002-7863 |
| DOIs | |
| Publication status | Published - 2024 |
Bibliographical note
Funding Information:
We thank the European Synchrotron Research Facility (CH-6518) and Synchrotron SOLEIL (20190807) for the experimental time. This research was supported by the EPSRC (grant number EP/V029347/1 and EP/W029057/1). M.L.B. was supported by the Analytical Chemistry Trust Fund and a Community for Analytical Measurement Science (CAMS) Fellowship. M.L.B. and T.G.B. were supported by a Royal Society of Chemistry Research Enablement Grant (E22-8595674725). M.S.H. and M.L.B. acknowledge a travel grant from CONEXS (EPSRC, EP/S022058/1). This work was supported by computing resources provided by the STFC Scientific Computing Department SCARF cluster, the University of Manchester Computational Shared Facility, and associated support services. We extend thanks to Timothy Bohdan at ID26 for his technical assistance, as well as to Patrick Colomp (ESRF) and Bruno Forgeat (SOLEIL) of the Radioprotection Services for their help at ID26 and MARS.
Publisher Copyright:
© 2024 The Authors. Published by American Chemical Society
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