Molecular Simulations of Aqueous Electrolytes: Role of Explicit Inclusion of Charge Transfer into Force Fields.

Abstract

We describe here simulations of aqueous salt solutions that are performed using an explicit charge transfer force field. The emphasis of the discussion is on the calculation of a dynamical property of the solutions: self-diffusion of water. While force fields that are based on pairwise additive potentials or on potentials with explicit inclusion of polarization or with scaled charges can provide at best a qualitative agreement with experiments, force fields with explicit inclusion of charge transfer can produce quantitative agreement with experiment for NaCl and KCl solutions. We argue that a force field with explicit charge transfer contains new physics absent in the previously used force fields described in recent reviews of molecular simulations of aqueous electrolytes.