title: DFT studies of uranyl acetate, carbonate, and malonate, complexes in solution.
abstract: The aim of this work is to demonstrate that theoretical chemistry can be used as a complementary tool in determining geometric parameters of a number of uranyl complexes in solution, which are not observable by experimental methods. In addition, we propose plausible structures with partial geometric data from experimental results. A gradient corrected DFT methodology with relativistic effects is used employing a COSMO solvation model. The theoretical calculations show good agreement with experimental X-ray and EXAFS data for the triacetato-dioxo-uranium(VI) and tricarbonato-dioxo-uranium(VI) complexes and are used to assign possible geometries for dicalcium-tricarbonato-dioxo-uranium(VI) and malonato-dioxo-uranium(VI) complexes. The results of this exercise indicate that carbonate bonding in these complexes is mainly bidentate and that hydroxo bridging plays a critical role in the stabilization of the polynuclear uranyl complexes.
authors.affiliation: Area de Gestió de Residus, Centre Tecnològic de Manresa, E-08240 Manresa, Spain.
authors.forename: Jordi
authors.initials: J
authors.lastname: Vázquez
authors.forename: Carles
authors.initials: C
authors.lastname: Bo
authors.forename: Josep Maria
authors.initials: JM
authors.lastname: Poblet
authors.forename: Joan
authors.initials: J
authors.lastname: de Pablo
authors.forename: Jordi
authors.initials: J
authors.lastname: Bruno