Generalized approach to global renormalization-group theory for fluids

The global renormalization-group theory (GRGT) for fluids is derived starting with the square-gradient approximation for the Helmholtz free energy functional such that any mean-field free energy density and direct correlation function can be employed. The new derivation uses Wilson's functions for representing density fluctuations, thereby relaxing the assumption of cosine variation of density fluctuations used in earlier approaches. The generality of the present approach is shown by deriving the relationships to the earlier developments. A qualitative way to infer the free parameters in the present form of GRGT is also suggested. The new theory is applied to square-well fluids of ranges 1.5 and 3.0 (in units of hard-sphere diameter) and Lennard-Jones fluids. It is shown that the present theory produces a flat isotherm in the two-phase region. Thus the theory accounts for fluctuations at all length scales and avoids the use of Maxwell's construction. An analysis of the liquid-vapor phase diagrams and the critical constants obtained for different potentials shows that, with a mean-field free energy density that is accurate away from the critical region and an appropriate coarse graining length for the mean-field theory, GRGT can provide results in good agreement with the simulation and experimental results.