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Glassiness and Heterogeneous Dynamics in Dense Solutions of Ring Polymers.

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Understanding how topological constraints affect the dynamics of polymers in solution is at the basis of any polymer theory and it is particularly needed for melts of rings. These polymers… Click to show full abstract

Understanding how topological constraints affect the dynamics of polymers in solution is at the basis of any polymer theory and it is particularly needed for melts of rings. These polymers fold as crumpled and space-filling objects and, yet, they display a large number of topological constraints. To understand their role, here we systematically probe the response of solutions of rings at various densities to "random pinning" perturbations. We show that these perturbations trigger non-Gaussian and heterogeneous dynamics, eventually leading to nonergodic and glassy behavior. We then derive universal scaling relations for the values of solution density and polymer length marking the onset of vitrification in unperturbed solutions. Finally, we directly connect the heterogeneous dynamics of the rings with their spatial organization and mutual interpenetration. Our results suggest that deviations from the typical behavior observed in systems of linear polymers may originate from architecture-specific (threading) topological constraints.

Keywords: dynamics dense; solutions ring; glassiness heterogeneous; heterogeneous dynamics; topological constraints; dense solutions

Journal Title: Physical review letters
Year Published: 2017

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