Generalized van der Waals theory. IV. Variational determination of the hard-sphere diameter

Abstract

The generalized van der Waals theory is here extended by incorporating the hard-sphere diameter as a variational parameter. Moreover, the entropy functional has been chosen so as to accurately reflect the density dependence of the excluded volume revealed by the hard-sphere equation of state. The combined effect of these two improvements yields a theory capable of describing the equation of state of the Lennard- Jones model of classical fluids to an accuracy comparable to that of the pair correlation theories. The results presented here include critical parameters and coexistence and vapour pressure curves.