Solvent Entropy in and Coarse-Graining of Polymer Lattice Models

TL;DR

This paper introduces a method to accurately incorporate solvent entropy into lattice models of polymers, improving coarse-graining and fluctuation representation for both homogeneous and inhomogeneous systems.

Contribution

It presents a quantitative coarse-graining strategy that properly accounts for solvent entropy and fluctuations in lattice models with multiple occupancy.

Findings

Corrects solvent entropy representation in lattice models.

Enables accurate coarse-graining of polymer systems.

Applicable to both homogeneous and inhomogeneous systems.

Abstract

The self- and mutual-avoiding walk used in conventional lattice models for polymeric systems requires that all lattice sites, polymer segments, and solvent molecules (unoccupied lattice sites) have the same volume. This incorrectly accounts for the solvent entropy (i.e., size ratio between polymer segments and solvent molecules), and also limits the coarse-graining capability of such models, where the invariant degree of polymerization controlling the system fluctuations is too small (thus exaggerating the system fluctuations) compared to that in most experiments. Here we show how to properly account for the solvent entropy in the recently proposed lattice models with multiple occupancy of lattice sites [Q. Wang, Soft Matter 5, 4564 (2009)], and present a quantitative coarse-graining strategy that ensures both the solvent entropy and the fluctuations in the original systems are properly accounted for using such lattice models. Although proposed based on homogeneous polymer solutions, our strategy is equally applicable to inhomogeneous systems such as polymer brushes immersed in a small-molecule solvent.