``Improved'' Free-Volume Theory of Liquids. IV. Supercells, Worms, and Tunnels

Abstract

The formalism for a ``supercell'' theory of liquids is presented. Conceptually, it is analogous to the scheme employed by Kirkwood in ``justifying'' the single-occupancy cell theory of Lennard-Jones and Devonshire. The attractive feature of the theory lies in its ability to handle the large density fluctuations which the single-occupancy theory is unable to treat adequately. The derivation of the numerically successful tunnel theory of Barker from our generalized supercell formalism by means of a certain number of well-defined approximations is given.