Linear viscoelasticity of semiflexible polymers with hydrodynamic interactions

Abstract

The linear viscoelastic response of single semiflexible polymer chains in the infinite-dilution limit is studied using Brownian dynamics simulations of coarse-grained bead–spring chains. The springs obey the FENE–Fraenkel force law, a bending potential is used to capture chain stiffness and hydrodynamic interactions are included through the Rotne–Prager–Yamakawa tensor. By calculating the relaxation modulus following a step strain, we demonstrate that the bead–spring chain behaves like an inextensible semiflexible rod over a wide time window with an appropriate choice of spring stiffness and chain extensibility. In the absence of hydrodynamic interactions, our results agree with the existing theoretical predictions for the linear viscoelastic response of free-draining, inextensible, semiflexible rods in the limit of infinite dilution. It is shown that at intermediate times, the stress relaxation modulus exhibits power law behaviour, with the exponent ranging from (−1/2) for flexible chains to (−5/4) for highly rigid chains. At long times, rigid chains undergo orientational relaxation, while flexible chains exhibit Rouse relaxation. Hydrodynamic interactions are found to affect the behaviour at intermediate and long times, with the difference in free-draining behaviour increasing with increasing chain flexibility. Computations of the frequency dependence of loss and storage moduli are found to be in good agreement with experimental data for a wide variety of systems involving semiflexible polymers of varying stiffness across a broad frequency range.