Topological free volume and quasi-glassy dynamics in the melt of ring polymers

Abstract

Motivated by recent observations that non-concatenated ring polymers in their dense solution exhibit a glass-like dynamics, we propose a free volume description of the motion of such rings based on the notion of topological volume. We first construct a phenomenological free energy which enables one to quantify the degree of topological crowding measured by the coordination number. Then we pinpoint a key role of the cooperative dynamics of neighboring rings, which is responsible for an anomalous dependence of the global structural relaxation (diffusion) time on ring length. Predictions on molecular weight dependence of both static (ring size, coordination number) and dynamic (relaxation time, diffusion coefficient) quantities are in very good agreement with reported numerical simulations. Throughout the discussion, the entanglement length Ne is assumed to be a unique characteristic length for the topological constraint, and hence, all the physical quantities are universally described in terms of the rescaled chain length N/Ne. Finally, we discuss how the dense solution of rings is analogous to yet different from ordinary glassy systems.