A new analytic statistical mechanical model for polar fluids

TL;DR

This paper introduces a new analytic statistical mechanical model for polar fluids that accurately predicts thermodynamic properties using Yukawa potentials and multipole interactions, with good agreement to experimental data.

Contribution

The paper develops a novel analytic model incorporating multiple Yukawa tails and electrostatic interactions for polar fluids, enabling direct calculation of thermodynamic properties.

Findings

Accurately predicts thermodynamic properties of argon, carbon dioxide, and methyl chloride.

Shows good agreement with experimental data using only potential parameters and multipole moments.

Provides analytic expressions for properties of both polar and non-polar fluids.

Abstract

A new analytic statistical mechanical model for polar fluids with an intermolecular pair potential consisting of a hard core and multiple attractive Yukawa tails has been developed. It includes all the leading terms in the orientationally averaged electrostatic energies up to quadrupole-quadrupole interactions. This model is capable of producing analytic expressions for all the thermodynamic properties of both non-polar and polar fluids. We have evaluated the Yukawa potential parameters to represent the dispersion potential from several methods and formulated other Yukawa potentials to represent electrostatic potentials in simple closed forms, which then could be calculated directly. Therefore, introducing an arbitrary number of Yukawa potentials does not introduce any further computational difficulty. Thermodynamic properties of three representative fluids (argon, carbon dioxide, and methyl chloride) are predicted with this model. The results indicate good agreement between experiment and the predictions from this model, given only the Yukawa intermolecular potential parameters and multipole moments.