Universality of dilute solutions of ring polymers in the thermal crossover region between $\theta$ and athermal solvents

TL;DR

This study uses Brownian dynamics simulations to explore the universal static and dynamic properties of dilute ring polymer solutions across the thermal crossover from $ heta$ to athermal solvents, revealing fundamental differences from linear polymers.

Contribution

It demonstrates the asymptotic constancy of the ratio of radius of gyration to hydrodynamic radius for ring polymers, unlike linear chains, and shows the independence of the stretch-to-radius ratio on solvent quality.

Findings

The ratio $U_{RD}$ converges to a constant for rings as $z o fty$.

The ratio $X/R_H$ is independent of $z$ for rings.

Distinct scaling behaviors of static and dynamic properties between rings and linear chains.

Abstract

Due to their unique topology of having no chain ends, dilute solutions of ring polymers exhibit behaviour 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 $\theta$ and athermal solvents, is studied here using Brownian dynamics simulations. The universal ratio $U_{\text{RD}}$ of the radius of gyration $R_g$ to the hydrodynamic radius $R_H$ is determined, and a comparative study of the swelling ratio $\alpha_g$ of the radius of gyration, the swelling ratio $\alpha_H$ of the hydrodynamic radius, and the swelling ratio $\alpha_X$ of the mean polymer stretch $X$ along the $x$-axis, for linear and ring polymers, is carried out. The ratio $U_{\text{RD}}$ for dilute ring polymer solutions is found to converge asymptotically to a constant value as $z \to \infty$, which is a major difference from the behaviour 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, $(X/R_H)$, 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.