Coarse-graining polymer solutions: a critical appraisal of single- and multi-site models

TL;DR

This paper critically reviews single- and multi-site coarse-grained models for polymer solutions, highlighting their advantages, limitations, and proposing a thermodynamically consistent multi-site approach to improve accuracy and transferability.

Contribution

It introduces a multi-site coarse-graining strategy that overcomes limitations of single-site models, enhancing thermodynamic consistency and transferability.

Findings

Zero-density models fail to predict fluid-fluid demixing accurately.

Density-dependent models underestimate polymer volume fractions at phase separation.

Multi-site models improve thermodynamic predictions and phase behavior accuracy.

Abstract

We critically discuss and review the general ideas behind single- and multi-site coarse-grained (CG) models as applied to macromolecular solutions in the dilute and semi-dilute regime. We first consider single-site models with zero-density and density-dependent pair potentials. We highlight advantages and limitations of each option in reproducing the thermodynamic behavior and the large-scale structure of the underlying reference model. As a case study we consider solutions of linear homopolymers in a solvent of variable quality. Secondly, we extend the discussion to multi-component systems presenting, as a test case, results for mixtures of colloids and polymers. Specifically, we found the CG model with zero-density potentials to be unable to predict fluid-fluid demixing in a reasonable range of densities for mixtures of colloids and polymers of equal size. For larger colloids, the polymer volume fractions at which phase separation occurs are largely overestimated. CG models with density-dependent potentials are somewhat less accurate than models with zero-density potentials in reproducing the thermodynamics of the system and, although they presents a phase separation, they significantly underestimate the polymer volume fractions along the binodal. Finally, we discuss a general multi-site strategy, which is thermodynamically consistent and fully transferable with the number of sites, and that allows us to overcome most of the limitations discussed for single-site models.