Self‐consistent field equations in the distribution function theory of polymeric liquids

Abstract

AbstractIn the distribution function approach to the conformational and thermodynamic properties of polymeric liquids site‐site (pair) distribution functions are essential components of the theory. These site‐site pair distribution functions are basically mean fields obeying integral equations. In our recent works, a set of self‐consistent field equations has been proposed for site‐site pair correlation functions which allow us to study conformational and thermodynamic properties of polymeric liquids. In this article, we present a short review of the theory and its applications to a number of aspects of polymeric liquids we have made until now. We also present a self‐consistent version of the polymer reference interaction site model where the integral equations for the intramolecular site‐site correlation functions are obtained from the Kirkwood hierarchy on the basis of the present theory. The present theory is shown to predict correctly the scaling properties associated with swollen and collapsed polymers in good and poor solvents, respectively. At finite densities, self‐consistent solutions of the intra‐ and intermolecular equations yield the structures and thermodynamics of polymer melts which are favorably compared with Monte Carlo simulation results. Self‐consistent theory results are found to be more accurate than the non‐self‐consistent approaches that use an ideal Gaussian chain conformation distribution function. © 1995 John Wiley & Sons, Inc.