Nonsphericalized Free Volumes for Hole Theories of Liquids

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Abstract
Free‐volume integrals for hole theories of liquids were calculated for some special cases by Monte Carlo numerical integration. The dependence of the free volume on the number of nearest neighbors is thus obtained. Only molecules interacting with a Lennard‐Jones potential and a temperature near the critical one have been considered. The results differ considerably from those of earlier theories, where spherical symmetry was assumed. However, the introduction of vacant cells (holes) does not improve the thermodynamic functions obtained with the cell theory of Lennard‐Jones and Devonshire.

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