The dielectric constant: reconciling simulation and experiment

Research output: Contribution to journalArticle

2 Citations (Scopus)

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.

LanguageEnglish
Article number084108
JournalJournal of Chemical Physics
Volume150
Issue number8
DOIs
Publication statusPublished - 26 Feb 2019

Fingerprint

Permittivity
permittivity
lead compounds
scaling
simulation
Experiments
predictions
Lead compounds
Potential energy surfaces
Dipole moment
dipole moments
methyl alcohol
potential energy
refractivity
Methanol
Refractive index
polarization
Polarization
liquids
electronics

Keywords

  • dielectric constants
  • polarisation effects
  • potential energy surface (PES)
  • dipole moment surface (DMS)

Cite this

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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.",
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The dielectric constant : reconciling simulation and experiment. / Jorge, Miguel; Lue, Leo.

In: Journal of Chemical Physics, Vol. 150, No. 8, 084108, 26.02.2019.

Research output: Contribution to journalArticle

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T1 - The dielectric constant

T2 - Journal of Chemical Physics

AU - Jorge, Miguel

AU - Lue, Leo

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AB - 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.

KW - dielectric constants

KW - polarisation effects

KW - potential energy surface (PES)

KW - dipole moment surface (DMS)

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