Perturbation theory for multipolar discrete fluids

Abstract

An analytical expression for the Helmholtz free energy of discrete multipolar potentials as a function of density, temperature, and intermolecular parameters is obtained as an extension of the multipolar square-well perturbation theory [A. L. Benavides, Y. Guevara, and F. del Río, Physica A 202, 420 (1994)]. The presented procedure is suitable for the description of a more general intermolecular potential model taking into account the overlap and dispersion forces through a discrete potential represented by a sequence of square-shoulders and wells, as well as electrostatic interactions. The main advantage of this approach is that since the Helmholtz free energy is given as an explicit expression in terms of the intermolecular parameters characterizing the interaction, the properties of interest can be easily obtained through usual thermodynamic relations. Besides, since a great variety of discretized potentials can be used with this equation of state, its applicability is very vast. By varying the intermolecular parameters, some illustrative cases are considered, and their phase diagrams are tested against available simulation data. It is found that this theoretical approach is able to reproduce qualitatively and quantitatively well the vapor-liquid equilibrium of the chosen potentials with different multipole moment of varied strengths, except in the critical region.