Heterogeneous Rouse Model Predicts Polymer Chain Translational Normal Mode Decoupling

Abstract

It has been known for 50 years that polymers exhibit chain normal mode decoupling upon approach to the glass transition, with chain dynamics exhibiting a weaker temperature dependence than segmental dynamics. Inspired by Sokolov and Schweizer’s suggestion that this thermorheological complexity is a consequence of dynamic heterogeneity in the supercooled state, we generalize the Rouse model to account for a distribution of segmental mobilities. The heterogeneous Rouse model (HRM) predicts chain translational normal mode decoupling as a manifestation of diffusion/relaxation decoupling (Stokes–Einstein breakdown)—a consequence of differences in how normal modes average over a distribution of segmental mobilities. Molecular dynamics simulations agree with theoretical predictions, with the HRM found to quantitatively predict deviations from Rouse scaling of the translational friction coefficient based on the observed degree of Stokes–Einstein breakdown.