Molecular dynamics simulations of aqueous NaCl and KCl solutions: effects of ion concentration on the single-particle, pair, and collective dynamical properties of of ions and water molecules

Abstract

We have performed a series of molecular dynamics simulations of aqueous NaCl and KCl solutions at different concentrations, ranging from 0 M to 4.5 M, to investigate the effects of ion concentration on the single-particle, pair, and collective dynamical properties of aqueous electrolyte solutions. The SPC/E model is used for water and the ions are modeled as charged Lennard-Jones particles. The single-particle dynamics is investigated by calculating the self-diffusion coefficients of ions and water molecules and also the orientational relaxation times. The pair dynamics is studied by evaluating the ion-water residence and water-water hydrogen bond time correlation functions. The relaxation of relative velocity autocorrelation function and the cross velocity correlation function of two hydrogen bonded water molecules are also investigated at varying ion concentration. Finally, we explore the collective dynamical properties by calculating the frequency dependent dielectric function and conductivity. It is found that the self and relative diffusion coeffcients decrease and the orientational relaxation times increase with ion concentration. The residence times of water molecules near ions and also the structural relaxation time of water-water hydrogen bonds show an increasing trend as the ion concentration is increased. The dielectric relaxation time is found to decrease with ion concentration for the solutions investigated here. The static conductivity of concentrated solutions shows significant departure from the Nernst-Einstein behavior due to formation of ion pairs. With an increase of frequency, the conductivity first increases substantially and then decreases at very high frequency. The initial increase of conductivity is attributed to the disruption of ion pairs on application of high frequency electric fields.