液体理论中的Kirkwood变分方法的推广

本文克服了Cohen理论的缺点,对液体理论中Kirkwood变分方法作了推广。经过这样推广,格胞模型理论就可以系统地考虑分子运动关联性的任何级近似。把所得结果应用到一维情形,得到的自由能是严格正确的。应用到三维情形,最低级近似得LJD结果,一级近似得Taylor结果。

AN EXTENSION OF KIRKWOOD'S VARIATIONAL METHOD IN THE THEORY OF LIQUIDS

Kirkwood's variational method in the theory of liquids is extended to more general cell model of liquids. The incompleteness in Cohen's theory is thus overcome. It appears that the present theory is able to treat systematically the correlation of molecular motion in the cell model to any degree of approximation. Applied to the one-dimensional case, the theory gives exact result for the free energy. In the three-dimensional case, the lowest order approximation leads to Kirkwood's result, and the first order approximation yields Taylor's result.