Cell and Cellhyphen;Cluster Models for Liquids

摘要

The theory of the cell model is developed in its most general form, allowing an arbitrary volume and a variable number of occupants to each cell. Kirkwood's principle of minimizing the free energy is used to determine the best cell distribution functions and thermodynamic functions. It is shown that the isotherms computed by Lennardhyphen;Jones and Devonshire are subject to two large but almost compensating corrections. It is proposed to eliminate the inconsistencies of the cell model by introducing de Boer's concept of cell clusters, which in principle allows an exact evaluation of the partition function. Numerical corrections for clusters of two cells are calculated and shown to be small in effect.