Single-chain dynamics in a semidilute polymer solution under steady shear

Abstract

We use Brownian dynamics computer simulations to investigate single-chain dynamics in a semidilute polymer solution undergoing a steady, uniform shear flow. In the presence of the shear flow, the system used in the present study exhibits anisotropic structure factors, often referred to as butterfly patterns, which rotate with increasing shear rate [P. P. Jose and G. Szamel, J. Chem. Phys. 127, 114905 (2007)]. The rotation of these patterns correlates with shear thinning of the solution. In order to elucidate the microscopic origin of this behavior, we have investigated the change in the single-chain dynamics in the solution: We have focused on the relaxation of the end-to-end vector, the Rouse modes, and the radius of gyration tensor. In equilibrium and for small shear rates, these quantities show double exponential relaxation. With increasing shear rate, they show oscillatory relaxation, which hints at the tumbling motion of the chain. In the high shear rate regime, the frequency of the oscillations of the end-to-end vector autocorrelation function shows a power law dependence on the shear rate. We have compared the single-chain dynamics in the semidilute solution with that in a dilute solution. An analysis of the instantaneous values of the radius of gyration tensor, the end-to-end distance, and the normal stress along the system's trajectory reveals a synchronization of the fluctuations of these quantities.