Dielectric Constants of Simple Liquids: Stockmayer and Ellipsoidal Fluids

• Published in: The journal of physical chemistry. B Vol. 114; no. 25; pp. 8431 - 8440
• Main Authors: Johnson, Lewis E, Barnes, Robin, Draxler, Thomas W, Eichinger, Bruce E, Robinson, Bruce H
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 01.07.2010
• Subjects: B: Statistical Mechanics, Thermodynamics, Medium Effects
• ISSN: 1520-6106; 1520-5207; 1520-5207
• DOI: 10.1021/jp1010605

Coarse-grained models of molecular interactions are of interest because they convey the essence of molecular interactions in simple and easy to understand form. However, coarse-grained models fail to adequately predict some material properties, such as the failure of the Stockmayer model to reproduce the dielectric behavior of highly polar liquids. We examine the behavior of the Stockmayer fluid over a range of dipole densities that covers known organic solvents, as well as that of an ellipsoidal Stockmayer-like fluid, using NVT rigid-body Monte Carlo simulations. Both fluids are examined under different electrostatic boundary conditions and ensemble sizes. While the Stockmayer model predicts that liquids of similar dipole density to acetonitrile would be ferroelectric and have a dielectric constant far higher than shown by experiment, the ellipsoidal model provides a better accounting of dielectric behavior. This result bodes well for the use of coarse-grained solvent models for large-scale simulations.