Perturbation theory for non-axial molecular fluids

The thermodynamic perturbation theory in which all angle-dependent interactions are considered as a perturbation of the central potential is applied to study the equilibrium properties of a fluid composed of non-axial molecules. The influence of a large number of anisotropic pair and three-body non-additive interactions have been taken into account. Using the same set of force parameters the calculation is made for gaseous pressure second and third virial coefficients and liquid phase thermodynamic properties (Helmholtz free-energy, configurational energy, pressure and entropy). It is shown that the non-axial approximation is an improvement over the axial one. Excellent agreement between theory and experiment is obtained for ethylene.