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Bounding [AnO 2 ] 2+ (An = U, Np) covalency by simulated O K-edge and An M-edge X-ray absorption near-edge spectroscopy †

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<mark>Journal publication date</mark>21/09/2023
<mark>Journal</mark>Physical Chemistry Chemical Physics
Issue number25
Number of pages8
Pages (from-to)3753-23760
Publication StatusPublished
Early online date24/08/23
<mark>Original language</mark>English


Restricted active space simulations are shown to accurately reproduce and characterise both O K-edge and U M -edge spectra of uranyl in excellent agreement with experimental peak positions and are extended to the Np analogue. Analysis of bonding orbital composition in the ground and O K-edge core-excited states demonstrates that metal contribution is underestimated in the latter. In contrast, An M -edge core-excited states produce bonding orbital compositions significantly more representative of those in the ground state. Quantum Theory of Atoms in Molecules analysis is employed to explain the discrepancy between K- and M-edge data and demonstrates that the location of the core-hole impacts the pattern of electron localisation in core-excited states. An apparent contradiction to this behaviour in neptunyl is rationalised in terms interelectronic repulsion between the unpaired 5f electron and the excited core-electron.