The dielectric constant : reconciling simulation and experiment

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Jorge, Miguel and Lue, Leo (2019) The dielectric constant : reconciling simulation and experiment. Journal of Chemical Physics, 150 (8). 084108. ISSN 0021-9606 (https://doi.org/10.1063/1.5080927)

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Abstract

In this paper, we present a simple correction scheme to improve predictions of dielectric constants by classical non-polarisable models. This scheme takes into account electronic polarisation effects, through the experimental refractive index of the liquid, and a possible mismatch between the potential energy surface and the dipole moment surface. We have described the latter effect by an empirical scaling factor on the point charges, the value of which was determined by fitting the dielectric constant of methanol. Application of the same scaling factor to existing benchmark datasets, comprising four different models and a wide range of compounds, led to remarkable improvements in the quality of the predictions. In particular, the observed systematic underestimation of the dielectric constant was eliminated by accounting for the two missing terms in standard models. We propose that this correction term be included in future development and validation efforts of classical non-polarisable models.

ORCID iDs

Jorge, Miguel ORCID logoORCID: https://orcid.org/0000-0003-3009-4725 and Lue, Leo ORCID logoORCID: https://orcid.org/0000-0002-4826-5337;
CORE (COnnecting REpositories)