Efficient simulations of mobility matrices for electrolytes by applying forces

Abstract

Ion drift velocities in response to electric fields are a critical attribute of battery electrolytes. Accurately predicting species mobilities in such systems is an important challenge for atomistic simulations. In this work, we investigate two organic liquid electrolytes: LiPF₆ dissolved in (a) dimethyl carbonate (DMC) and (b) a mixture of DMC and ethylene carbonate (EC). We compare two approaches to measure mobilities: observing center of mass diffusion with no forces applied, and observing species drift in response to external forces. The two approaches are related by the fluctuation–dissipation theorem, but they are not equally efficient computationally. We argue that statistical errors of the two methods scale differently with system size and simulation run time. In a head-to-head test, we apply both methods to LiPF₆ in DMC in multiple simulations with the same size and run time. The drift method gives a much smaller variance in repeated measurements than the diffusion method, and should be preferred in practice.