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Non-covalent interactions of uranyl complexes: a theoretical study

Platts, James A. ORCID: and Baker, Robert J. 2018. Non-covalent interactions of uranyl complexes: a theoretical study. Physical Chemistry Chemical Physics 20 (22) , pp. 15380-15388. 10.1039/C8CP02444H

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We report a set of theoretical calculations designed to examine the potential of model uranyl complexes to participate in hydrogen- and halogen-bonding. Potential energy scans for the interaction of [UO2Cl2(H2O)3] and [UO2(NCSe)2(H2O)3] with water demonstrate that uranyl is a weak hydrogen bond acceptor, but that equatorially coordinated water is a strong hydrogen bond donor. These predictions are supported by a survey of contacts reported in the Cambridge Structural Database. At the minima of each scan, we show that the interaction energy is only weakly dependent on the choice of theoretical method, with standard density functional theory methods comparing well with coupled-cluster, MP2 and double-hybrid predictions. Geometry optimisation of a 1:1 uranyl:water complex results in a cyclic structure, in which vibrational frequencies, atoms-in-molecules and natural bond orbital analysis support the weakness of U—Oyl as acceptor. The origin of this behaviour is traced to the electronic structure of uranyl, and in particular covalency in the U—Oyl bonds resulting from donation into formally empty 5f and 6d orbitals on U.

Item Type: Article
Date Type: Published Online
Status: Published
Schools: Chemistry
Advanced Research Computing @ Cardiff (ARCCA)
Publisher: Royal Society of Chemistry
ISSN: 1463-9076
Funders: Cardiff University
Date of First Compliant Deposit: 15 May 2018
Date of Acceptance: 15 May 2018
Last Modified: 08 Nov 2023 08:42

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