Estimates of Electrical Conductivity from Molecular Dynamics Simulations: How to Invest the Computational Effort

Abstract

Although the electrical conductivity of an electrolyte can be estimated from the molecular dynamics trajectory, it is often a challenging task because of the need to obtain a substantial amount of data to ensure sufficient averaging. Here, we present an analysis on the convergence of results with the number of simulated trajectories. A series of molecular dynamics simulations have been performed for a model electrolyte (NaCl in water) and the Einstein relation has been used to calculate the electrical conductivity. The standard deviation of the conductivity estimates is relatively large compared to the mean value, and it has been shown that the off-diagonal contributions to the collective displacement of ions are responsible for large deviations between systems. It has been found that about 40 independent MD simulations may be required to reduce the errors. A procedure to improve the final estimate of the conductivity has been proposed.