Dielectric Decrement for Aqueous NaCl Solutions: Effect of Ionic Charge Scaling in Nonpolarizable Water Force Fields.

Abstract

We investigate the dielectric constant and the dielectric decrement of aqueous NaCl solutions by means of molecular dynamic simulations. We thereby compare the performance of four different force fields and focus on disentangling the origin of the dielectric decrement and the influence of scaled ionic charges, as often used in nonpolarizable force fields to account for the missing dynamic polarizability in the shielding of electrostatic ion interactions. Three of the force fields showed excessive contact ion pair formation, which correlates with a reduced dielectric decrement. In spite of the fact that the scaling of charges only weakly influenced the average polarization of water molecules around an ion, the rescaling of ionic charges did influence the dielectric decrement, and a close-to-linear relation of the slope of the dielectric constant as a function of concentration with the ionic charge was found.