Investigation of ligand exchange reactions in aqueous uranyl carbonate complexes using computational approaches

Slimane Doudou, Krishnamoorthy Arumugam, David J. Vaughan, Francis R. Livens, Neil A. Burton

    Research output: Contribution to journalArticlepeer-review

    Abstract

    Carbonate anion exchange reactions with water in the uranyl-carbonate and calcium-uranyl-carbonate aqueous systems have been investigated using computational methods. Classical molecular dynamics (MD) simulations with the umbrella sampling technique were employed to determine potentials of mean force for the exchange reactions of water and carbonate. The presence of calcium counter-ions is predicted to increase the stability of the uranyl-carbonate species in accordance with previous experimental observations. However, the free energy barrier to carbonate exchange with water is found to be comparable both in the presence and absence of calcium cations. Possible implications of these results for uranyl adsorption on mineral surfaces are discussed. Density functional theory (DFT) calculations were also used to confirm the trends observed in classical molecular dynamics simulations and to corroborate the validity of the potential parameters employed in the MD scheme. © the Owner Societies.
    Original languageEnglish
    Pages (from-to)11402-11411
    Number of pages9
    JournalPhysical Chemistry Chemical Physics
    Volume13
    Issue number23
    DOIs
    Publication statusPublished - 21 Jun 2011

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