Swelling of two-dimensional polymer rings by trapped particles.

The mean area of a two-dimensional Gaussian ring of N monomers is known to diverge when the ring is subject to a critical pressure differential, p c ~ N -1. In a recent publication (Eur. Phys. J. E 19, 461 (2006)) we have shown that for an inextensible freely jointed ring this divergence turns into a second-order transition from a crumpled state, where the mean area scales as [A]~N-1, to a smooth state with [A]~N(2). In the current work we extend these two models to the case where the swelling of the ring is caused by trapped ideal-gas particles. The Gaussian model is solved exactly, and the freely jointed one is treated using a Flory argument, mean-field theory, and Monte Carlo simulations. For a fixed number Q of trapped particles the criticality disappears in both models through an unusual mechanism, arising from the absence of an area constraint. In the Gaussian case the ring swells to such a mean area, [A]~ NQ, that the pressure exerted by the particles is at p c for any Q. In the freely jointed model the mean area is such that the particle pressure is always higher than p c, and [A] consequently follows a single scaling law, [A]~N(2) f (Q/N), for any Q. By contrast, when the particles are in contact with a reservoir of fixed chemical potential, the criticality is retained. Thus, the two ensembles are manifestly inequivalent in these systems.