title: Primitive model for cation hydrolysis: a molecular-dynamics study.
abstract: A model of primitive cation MZ+ in water is introduced in order to clarify the influence of ion charge on the hydration structure and dynamic properties of highly charged cations in aqueous solutions. A flexible nonconstrained model for water molecules is used. The considered model in the case of monovalent cation M+ reduces to the realistic model for the hydration structure of Na+. It is shown that for divalent ion M2+ the strong cation-water electrostatic interaction leads to the formation of stable structures constituted by six water molecules octahedrally arranged around the cation. The cation-oxygen attraction and cation-hydrogen repulsion modify the octahedral hydration configuration of the model cations M3+ and M4+ and additional water molecules can join the hydration shell. The increase of cation charge results in the increase of O-H bond length of water molecules in the cation hydration shell. Further increase of ion-water electrostatic interaction causes the loss of some protons from the hydration shell of cations M4+, M5+, and M6+ that is interpreted as a cation hydrolysis effect. For a correct description of this phenomenon the considered model is improved by modeling the effects of the charge redistribution between hydrolysis products, which essentially modified and stabilized the hydrated-hydrolyzed structure of cation. The influence of cation charge on dynamical properties of cation MZ+ and oxygens in its hydration shell was investigated and analyzed.
authors.affiliation: Institute for Condensed Matter Physics, National Academy of Sciences of Ukraine, 1 Svientsitskii Street, 79011 Lviv, Ukraine. holovko@icmp.lviv.ua
authors.forename: M
authors.initials: M
authors.lastname: Holovko
authors.forename: M
authors.initials: M
authors.lastname: Druchok
authors.forename: T
authors.initials: T
authors.lastname: Bryk