title: Effect of uranyl ion concentration on structure and dynamics of aqueous uranyl solution: a molecular dynamics simulation study.
abstract: The effect of uranyl ion concentration on structure and dynamics of aqueous solutions of uranyl ions is investigated by molecular dynamics simulations. In order to get an idea about the effect of concentration of uranyl ions on local structural arrangements of water molecules around the uranyl ion, radial distribution functions of water molecules around the uranyl ion are analyzed for aqueous uranyl solutions of various concentrations. The concentration effect on translational dynamics has also been analyzed by calculating diffusion coefficients of uranyl ion, water, and nitrate ions in solution from their respective mean squared displacements. Mobility of water as well as uranyl ions has been found to decrease with increasing concentration of the uranyl ions. Orientational dynamics of water about different molecular axes of water have also been analyzed and decreasing orientational mobility of water with increasing uranyl concentration has been found. In order to get further insight into origin of slowing down of the translational mobility of water molecules with increasing uranyl ion concentration, two separate effects namely long-range effect of uranyl ions on the dynamics of water molecules beyond the solvation shell and short-range effect involving dynamics of solvation shell water have been analyzed. It is found that long-range effect is responsible for the slowing down of translational dynamics of water molecules in the presence of uranyl ions.
authors.affiliation: Radiation Safety Systems Division and ‡Theoretical Chemistry Section, Bhabha Atomic Research Centre , Mumbai, 400 085, India.
authors.forename: Manish
authors.initials: M
authors.lastname: Chopra
authors.forename: Niharendu
authors.initials: N
authors.lastname: Choudhury