Equilibrium theory of fluids in the presence of three-body forces

Abstract

Using the functional differentiation and topological reduction technique, we derive effective pair potentials to describe the correlation functions and thermodynamic properties of fluids in the presence of three-body forces. Relations between effective pair potentials derived from different properties are discussed. The pair correlation function is calculated using the Percus-Yevick integral equation theory and the hypernetted chain integral equation perturbation theory, the results are reported for neon, argon and xenon. Monte Carlo simulation is also done for Xe using the effective pair potential. The agreement found between the pair correlation function calculated from the integral equation perturbation theory and Monte Carlo simulation is good. The effect of the triple dipole and dipole-dipole-quadrupole interactions on the structure of fluid is found to be very small except near the first peak. We, however, except the sizable change in the structure factor S(q) for q < 1.0 Å⁻¹. The effect of the three-body interactions on the thermodynamic properties like internal energy and pressure is always measurable.