Self-diffusion coefficients of ions in electrolyte solutions by nonequilibrium Brownian dynamics

Abstract

The self-diffusion coefficients of the ions in a model electrolyte solution are calculated with a novel implementation of the nonequilibrium Brownian dynamics technique. The ions are coupled to an external color field E by color charges in such a way that each ionic species as a whole is electrically neutral to E. The ion–ion forces are not directly affected by the color charges or E. The method is tested on a model of a 1 M NaCl aqueous solution without hydrodynamic interactions and the results are compared with those of a previous equilibrium simulation for the same model system. The self-diffusion coefficients of Na+ and Cl− are determined with 2%–3% accuracy and, within this margin, agree with the results of the equilibrium simulation obtained with more than twice the computational effort. Furthermore, within the range of field strengths studied, the average color flows depend linearly on E.