Effects of chain resolution on the configurational and rheological predictions from Brownian dynamics simulations of an isolated polymer chain in flow

TL;DR

This study investigates how the level of chain discretization in Brownian dynamics simulations affects the accuracy of predicting polymer behavior in flow, focusing on configuration and rheological properties.

Contribution

It provides a detailed comparison of transient and steady-state behaviors across different chain discretizations, highlighting the limits of bead-spring models.

Findings

Differences in stress and viscosity predictions at high flow rates.

Identification of the minimum number of Kuhn steps for accurate spring law representation.

Quantitative analysis of discretization effects on polymer simulation accuracy.

Abstract

A reasonably accurate representation of a polymer chain is provided by beads connected with rods, or stiff, inextensible springs that mimic a single Kuhn step. Due to high computational cost, coarse-grained bead-spring models are used in typical applications, where each spring is supposed to replace several Kuhn steps. Earlier investigations indicate that the BD simulation predictions of the steady state in different flows, with these different levels of discretization, are largely qualitatively similar. However, subtle quantitative differences exist even for the steady states. In this study, we perform a detailed analysis of the behavioral differences arising out of the varying degrees of chain discretization, ranging from one to several hundred Kuhn steps. We compare the transient and steady behavior of both configuration and rheological properties for a single chain in uniaxial extension and steady shear flow. Our analysis highlights differences, particularly in the stress and viscosity values, obtained at intermediate and high flow rates, between the bead-rod and bead-spring models. Such a thorough understanding helps to provide an estimate of the best possible bead-spring representation for an underlying polymer chain in a given application. Additionally, we also investigate the limit of break-down of the spring laws i.e. the minimum number of Kuhn steps that a spring can mimic faithfully.