Ion hydration and associated defects in hydrogen bond network of water: observation of reorientationally slow water molecules beyond first hydration shell in aqueous solutions of MgCl2.

Abstract

Effects of the presence of ions, at moderate to high concentrations, on dynamical properties of water molecules are investigated through classical molecular dynamics simulations using two well-known nonpolarizable water models. Simulations reveal that the presence of magnesium chloride (MgCl(2)) induces perturbations in the hydrogen bond network of water leading to the formation of bulklike domains with ''defect sites'' on boundaries of such domains: water molecules at such defect sites have less number of hydrogen bonds than those in bulk water. Reorientational autocorrelation functions for dipole vectors of such defect water molecules are computed at different concentrations of ions and compared with system of pure water. Earlier experimental and simulation studies indicate significant differences in reorientational dynamics for water molecules in the first hydration shell of many dissolved ions. Results of this study suggest that defect water molecules, which are beyond the first hydration shells of ions, also experience significant slowing of reorientation times as a function of concentration in the case of MgCl(2). However, addition of cesium chloride (CsCl) to water does not perturb the hydrogen bond network of water significantly even at higher concentrations. This difference in behavior between MgCl(2) and CsCl is consistent with the well-known Hofmeister series.