title: The structural influence of Ca(2+) counter-ions on uranyl(VI) tricarbonate in aqueous solution.
abstract: The presented study elucidates the influence of calcium(II) counter-ions on the structure of the environmentally relevant uranyl tricarbonates using hybrid quantum mechanical/molecular mechanical (QM/MM) MD simulations. Since experimental investigations may be subject to limitations in detecting the presence of counter-ions in solution, the present study is of importance to obtain a profound understanding of the effects counter-ions may have on coordination complexes. It can be concluded from the obtained simulation data that two calcium(II) ions are essential for stabilizing the experimentally observed uranyl tricarbonate complex in aqueous solution. Including only one calcium(II) ion in the coordination sphere was found to be insufficient to form a six-fold equatorial coordination of carbonates, but a five-fold coordination is adopted similar to the counter-ion free case in aqueous solution reported in a previous study.
authors.affiliation: Theoretical Chemistry Division Institute of General, Inorganic and Theoretical Chemistry University of Innsbruck, Innrain 80-82, A-6020 Innsbruck, Austria. T.Hofer@uibk.ac.at.
authors.forename: Andreas O
authors.initials: AO
authors.lastname: Tirler
authors.affiliation: Theoretical Chemistry Division Institute of General, Inorganic and Theoretical Chemistry University of Innsbruck, Innrain 80-82, A-6020 Innsbruck, Austria. T.Hofer@uibk.ac.at.
authors.forename: Thomas S
authors.initials: TS
authors.lastname: Hofer