Reparameterization of Polarizable Force Fields for Studying Ion Transfer across Liquid-Liquid Interfaces.

Abstract

We have developed a general scheme for refining classical polarizable molecular dynamics (MD) force fields that can accurately describe the molecular interactions in systems with liquid-liquid interfaces. While ab initio MD (AIMD) simulations can naturally describe molecular interactions, they are often so computationally expensive that simulating large system sizes and/or long time scales is usually infeasible. To resolve this, we parameterized efficient and accurate classical polarizable force fields that use AIMD reference data by minimizing both the relative entropy and the root mean squared deviation in atomic forces. We utilized our new multiscale models to study chloride ion transfer across the water-dichloromethane (DCM) interface with and without the tetraethylammonium cation as the phase-transfer catalyst. Our calculated free-energy barrier for the water-DCM interface is consistent with the other reported simulation results. We further analyzed the ion-transfer process by studying the hydration shell structures around the chloride ion and the ion-pair formation to better understand the mechanism. We observed that electronic polarizability is an important factor for the studied phase-transfer catalyst to lower the free-energy barrier of the ion transfer. Using the water-benzene interface system as an additional example, we show that our parameterization scheme provides a general route for modeling different liquid-liquid interface systems even when the experimental data or force field parameters are not readily available.