Universality of dilute solutions of ring polymers in the thermal crossover region between θ and athermal solvents

Abstract

Due to their unique topology of having no chain ends, dilute solutions of ring polymers exhibit behavior distinct from their linear chain counterparts. The universality of their static and dynamic properties, as a function of solvent quality z in the thermal crossover regime between θ and athermal solvents, is studied here using Brownian dynamics simulations. The universal ratio URD of the radius of gyration Rg to the hydrodynamic radius RH is determined, and a comparative study of the swelling ratio αg of the radius of gyration, the swelling ratio αH of the hydrodynamic radius, and the swelling ratio αX of the mean polymer stretch X along the x-axis, for linear and ring polymers, is carried out. The ratio URD for dilute ring polymer solutions is found to converge asymptotically to a constant value as z→∞, which is a major difference from the behavior of solutions of linear chains, where no such asymptotic limit exists. Additionally, the ratio of the mean stretch along the x-axis to the hydrodynamic radius, (X/RH), is found to be independent of z for polymeric rings, unlike in the case for linear polymers. These results indicate a fundamental difference in the scaling of static and dynamic properties of rings and linear chains in the thermal crossover regime.