Benchmarks and Dielectric Constants for Reparametrized OPLS and Polarizable Force Field Models of Chlorinated...

The knowledge of dielectric response properties of the environment is of paramount importance in many theoretical embedding methods and studies of solutes and of catalytic sites and processes in condensed phases. In particular, the realistic embedding of active sites into solid/liquid and liquid/liquid interfaces is a crucial point in the context of modeling energy conversion (e.g., electrochemical, photochemical, power-to-X) processes. Recently, the finding that the dielectric permeability of liquids near solid/liquid interfaces is far from being constant but deviates strongly from the bulk value within several nanometers from the interface has raised the interest in a more fundamental understanding of the response properties near interfaces. As these questions are hard to study experimentally, reliable theoretical models are required. Here we describe a careful first-principles based reparametrization of nonpolarizable molecular mechanics force fields for a class of technological relevant organic chlorinated hydrocarbon solvents which are immiscible with water. For the solvent 1,2-dichloroethane (1,2-DCE) we also present a new polarizable force field based on the Drude oscillator model. Its parametrization needs particular attention to avoid unphysical couplings between the internal torsional degree of freedom and the Drude oscillators, which could severely skew the response properties. The performance of this new set of force fields is critically assessed based on a comprehensive molecular dynamics study.