Determination of Uranium Central-Field Covalency with 3d4f Resonant Inelastic X-ray Scattering

Timothy G. Burrow, Nathan M. Alcock, Myron S. Huzan, Maja A. Dunstan, John A. Seed, Blanka Detlefs, Pieter Glatzel, Myrtille O.J.Y. Hunault, Jesper Bendix, Kasper S. Pedersen*, Michael L. Baker*

*Corresponding author for this work

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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.

Original languageEnglish
JournalJournal of the American Chemical Society
Volume146
Issue number32
Pages (from-to)22570-22582
ISSN0002-7863
DOIs
Publication statusPublished - 14 Aug 2024

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