Analytical coarse-grained description for polymer melts

Abstract

Starting from the Ornstein-Zernike equation the authors derive an analytical theory, at the level of pair correlation functions, which coarse grains polymer melts into liquids of interacting soft colloidal particles. Since it is analytical, the presented coarse-graining approach will be useful in developing multiscale modeling procedures to simulate complex fluids of macromolecules. The accuracy of the theory is tested by its capacity to reproduce the liquid structure, as given by the center-of-mass intermolecular total pair correlation function. The theory is found to agree well with the structure predicted by molecular dynamics simulations of the liquid described at the united atom level as well as by molecular dynamics simulations of the liquid of interacting colloidal particles. The authors perform simulations of the liquid of interacting colloidal particles having as input the potential obtained from their analytical total pair correlation function by enforcing the hypernetted-chain closure approximation. Tests systems are polyethylene melts of chains with increasing degrees of polymerization and polymer melts of chains with different chemical architectures. They also discuss the effect of adopting different conventional approximations for intra- and intermolecular monomer structure factors on the accuracy of the coarse-graining procedure, as well as the relevance of higher-order corrections to their expression.