Force Field Benchmark of the TraPPE_UA for Polar Liquids: Density, Heat of Vaporization, Dielectric Constant, Surface Tension, Volumetric Expansion Coefficient, and Isothermal Compressibility

• Published in: The journal of physical chemistry. B Vol. 122; no. 5; pp. 1669 - 1678
• Main Authors: Núñez-Rojas, Edgar, Aguilar-Pineda, Jorge Alberto, Pérez de la Luz, Alexander, de Jesús González, Edith Nadir, Alejandre, José
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 08.02.2018
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/acs.jpcb.7b10970

The transferable potential for a phase equilibria force field in its united-atom version, TraPPE_UA, is evaluated for 41 polar liquids that include alcohols, thiols, ethers, sulfides, aldehydes, ketones, and esters to determine its ability to reproduce experimental properties that were not included in the parametrization procedure. The intermolecular force field parameters for pure components were fit to reproduce experimental boiling temperature, vapor–liquid coexisting densities, and critical point (temperature, density, and pressure) using Monte Carlo simulations in different ensembles. The properties calculated in this work are liquid density, heat of vaporization, dielectric constant, surface tension, volumetric expansion coefficient, and isothermal compressibility. Molecular dynamics simulations were performed in the gas and liquid phases, and also at the liquid–vapor interface. We found that relative error between calculated and experimental data is 1.2% for density, 6% for heat of vaporization, and 6.2% for surface tension, in good agreement with the experimental data. The dielectric constant is systematically underestimated, and the relative error is 37%. Evaluating the performance of the force field to reproduce the volumetric expansion coefficient and isothermal compressibility requires more experimental data.