Onset of glassiness in two-dimensional ring polymers: Interplay of stiffness and crowding

Abstract

The effect of ring stiffness and pressure on the glassy dynamics of a thermal assembly of two-dimensional ring polymers is investigated using extensive coarse-grained molecular dynamics simulations. In all cases, dynamical slowing down is observed with increasing pressure, and thereby, a phase space for equilibrium dynamics is identified in the plane of the obtained monomer density and ring stiffness. When the rings are highly flexible, i.e., have low ring stiffness, glassiness sets in via the crowding of crumpled polymers, which take on a globular form. In contrast, at large ring stiffness, when the rings tend to have large asphericity under compaction, we observe the emergence of local domains having orientational ordering at high pressures. Therefore, our simulations highlight how varying the deformability of rings leads to contrasting mechanisms in driving the system toward the glassy regime.