A polarization-consistent model for alcohols to predict solvation free energies

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Barrera, Maria Cecilia and Jorge, Miguel (2020) A polarization-consistent model for alcohols to predict solvation free energies. Journal of Chemical Information and Modeling, 60 (3). pp. 1352-1367. ISSN 1549-9596 (https://doi.org/10.1021/acs.jcim.9b01005)

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Abstract

Classical nonpolarizable models, normally based on a combination of Lennard-Jones sites and point charges, are extensively used to model thermodynamic properties of fluids, including solvation. An important shortcoming of these models is that they do not explicitly account for polarization effects, i.e., a description of how the electron density responds to changes in the molecular environment. Instead, polarization is implicitly included, in a mean-field sense, into the parameters of the model, usually by fitting to pure liquid properties (e.g., density). This causes problems when trying to describe thermodynamic properties that involve a change of phase (e.g., enthalpy of vaporization), that directly depend on the electronic response of the medium (e.g., dielectric constant), and that require mixing or solvation in different media (e.g., solvation free energies). Fully polarizable models present a natural route for addressing these limitations but at the price of a much higher computational cost. In this work, we combine the best of those two approaches by running fast simulations using nonpolarizable models and applying post facto corrections to the computed properties in order to account for the effects of polarization. By applying this new paradigm, a new united-atom force field for alcohols is developed that is able to predict both pure liquid properties, including dielectric constant, and solvation free energies in different solvents with a high degree of accuracy. This paves the way for the development of a generic classical nonpolarizable force field that can predict solvation of drug-like molecules in a variety of solvents.

ORCID iDs

Barrera, Maria Cecilia and Jorge, Miguel ORCID logoORCID: https://orcid.org/0000-0003-3009-4725;
CORE (COnnecting REpositories)