Simple corrections for the static dielectric constant of liquid mixtures from model force fields

Cardona, Javier and Jorge, Miguel and Lue, Leo (2020) Simple corrections for the static dielectric constant of liquid mixtures from model force fields. Physical Chemistry Chemical Physics, 22 (38). pp. 21741-21749. ISSN 1463-9076 (https://doi.org/10.1039/D0CP04034G)

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Abstract

Pair-wise additive force fields provide fairly accurate predictions, through classical molecular simulations, for a wide range of structural, thermodynamic, and dynamical properties of many materials. However, one key property that has not been well captured is the static dielectric constant, which characterizes the response of a system to an applied electric field and is important in determining the screening of electrostatic interactions through a system. A simple correction has been found to provide a relatively robust method to improve the estimate of the static dielectric constant from molecular simulations for a broad range of compounds. This approach accounts for the electronic contribution to molecular polarizability and assumes that the charges that couple a molecule to an applied electric field are proportional to the effective force field charges. In this work, we examine how this correction performs for systems at different temperatures and for binary mixtures. Using a value for the electronic polarizability, based on the experimental index of refraction, and a charge scaling factor, determined at a single temperature, we find that the static dielectric constant can be predicted remarkably well, in comparison to the experimentally measured values. This provides good evidence that the effective charges that appear in pair-wise additive force fields developed to reproduce the potential energy surface of a system are not the same as those that determine the static dielectric constant; however, they can be captured in a relatively simple manner, which is dependent on the particular force field.

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