Improved renormalization group theory for critical asymmetry of fluids

J Chem Phys. 2013 Sep 28;139(12):124103. doi: 10.1063/1.4821599.

Abstract

We develop an improved renormalization group (RG) approach incorporating the critical vapor-liquid equilibrium asymmetry. In order to treat the critical asymmetry of vapor-liquid equilibrium, the integral measure is introduced in the Landau-Ginzbug partition function to achieve a crossover between the local order parameter in Ising model and the density of fluid systems. In the implementation of the improved RG approach, we relate the integral measure with the inhomogeneous density distribution of a fluid system and combine the developed method with SAFT-VR (statistical associating fluid theory of variable range) equation of state. The method is applied to various fluid systems including square-well fluid, square-well dimer fluid and real fluids such as methane (CH4), ethane (C2H6), trifluorotrichloroethane (C2F3Cl3), and sulfur hexafluoride (SF6). The descriptions of vapor-liquid equilibria provided by the developed method are in excellent agreement with simulation and experimental data. Furthermore, the improved method predicts accurate and qualitatively correct behavior of coexistence diameter near the critical point and produces the non-classical 3D Ising criticality.