Fluids of semiflexible ring polymers: effective potentials and clustering

Abstract

We present a computational investigation of the structural properties of a fluid of semiflexible ring polymers. Stiffness is introduced by implementing intramolecular barriers. Because of these barriers, shrinkage of the rings is energetically unfavourable, and the ring size can exhibit a non-monotonic density dependence. At high concentrations the rings can swell and adopt open configurations that facilitate interpenetration and clustering. We obtain effective potentials between the centers-of-mass of the rings at infinite dilution, and explore their validity over the whole range of concentrations. Except for the limit of small rings, the effective fluid of ultrasoft particles provides a good description of the real system over a considerable range of densities, even above the overlap concentration. In particular the clustering behaviour predicted by the effective description is observed in the real system for a certain range of molecular masses. However, the effective description is incomplete. Inspection of the clusters of real rings reveals that these can arrange in a complex disordered phase formed by long columns of oblate rings, which are penetrated by bundles of elongated prolate rings. These anisotropic features of the real system are not captured by the standard effective approach, which only considers macromolecular centers-of-mass. This suggests the need to include the relative orientation between rings in the effective potentials. This journal is © 2013 The Royal Society of Chemistry.