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Research output: Contribution to Journal/Magazine › Journal article › peer-review
Research output: Contribution to Journal/Magazine › Journal article › peer-review
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TY - JOUR
T1 - Bounding [AnO 2 ] 2+ (An = U, Np) covalency by simulated O K-edge and An M-edge X-ray absorption near-edge spectroscopy †
AU - Stanistreet-Welsh, Kurtis
AU - Kerridge, Andrew
PY - 2023/9/21
Y1 - 2023/9/21
N2 - 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.
AB - 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.
U2 - 10.1039/d3cp03149g
DO - 10.1039/d3cp03149g
M3 - Journal article
VL - 2023
SP - 3753
EP - 23760
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 25
ER -