What is the optimal dipole moment for non-polarizable models of liquids?

Jorge, Miguel and Barrera, Maria Cecilia and Milne, Andrew W. and Ringrose, Chris and Cole, Daniel J. (2023) What is the optimal dipole moment for non-polarizable models of liquids? Journal of Chemical Theory and Computation, 19 (6). pp. 1790-1804. ISSN 1549-9618 (https://doi.org/10.1021/acs.jctc.2c01123)

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Abstract

In classical nonpolarizable models, electrostatic interactions are usually described by assigning fixed partial charges to interaction sites. Despite the multitude of methods and theories proposed over the years for partial charge assignment, a fundamental question remains─what is the correct degree of polarization that a fixed-charge model should possess to provide the best balance of interactions (including induction effects) and yield the best description of the potential energy surface of a liquid phase? We address this question by approaching it from two separate and independent viewpoints: the QUantum mechanical BEspoke (QUBE) approach, which assigns bespoke force field parameters for individual molecules from ab initio calculations with minimal empirical fitting, and the Polarization-Consistent Approach (PolCA) force field, based on empirical fitting of force field parameters with an emphasis on transferability by rigorously accounting for polarization effects in the parameterization process. We show that the two approaches yield consistent answers to the above question, namely, that the dipole moment of the model should be approximately halfway between those of the gas and the liquid phase. Crucially, however, the reference liquid-phase dipole needs to be estimated using methods that explicitly consider both mean-field and local contributions to polarization. In particular, continuum dielectric models are inadequate for this purpose because they cannot account for local effects and therefore significantly underestimate the degree of polarization of the molecule. These observations have profound consequences for the development, validation, and testing of nonpolarizable models.

ORCID iDs

Jorge, Miguel ORCID logoORCID: https://orcid.org/0000-0003-3009-4725, Barrera, Maria Cecilia, Milne, Andrew W. ORCID logoORCID: https://orcid.org/0000-0002-0938-2282, Ringrose, Chris and Cole, Daniel J.;
CORE (COnnecting REpositories)