Statistical Mechanics of Linear Molecules. IV. Nonspherical Polar Molecules

摘要

A modified form of the Stockmayer potential for polar molecules is utilized to calculate: pair correlation functions in the limit of zero density, ordinary second virial coefficients, and dielectric second virial coefficients. The potential function is modified by allowing the dispersionndash;repulsion part of the energy to be that for a linear symmetric molecule whose potential energy is represented by Lennardhyphen;Jones functions for the two ldquo;atomsrdquo; in the molecule interacting with the two ldquo;atomsrdquo; in neighboring molecules. This is combined with an ideal dipolendash;dipole energy to give the overhyphen;all potential function. Changes in the statistical properties are calculated as a function of the molecular length, and results are presented which indicate that the ordinary second virial coefficients change by moderate amounts, but that the dielectric second virial coefficient is strikingly affected by the introduction of nonspherical molecular shapes.