Ring polymers are much stronger depleting agents than linear ones

Abstract

We investigate the conformations and shapes of circular polymers close to planar, hard walls as well as the ensuing ring–wall and polymer-induced wall–wall interactions in ring polymer solutions. We derive, by means of Monte Carlo simulations, the effective interaction potential between the centres of mass of flexible, unknotted ring polymers and a hard wall for different polymerisation degrees N. Adopting the coarse-grained description of ring polymers as ultrasoft, penetrable spheres, mean-field density functional theory is then employed in order to examine ring polymer solutions under confinement. We demonstrate that, below the semi-dilute regime, ring polymers structure close to walls much more strongly than their linear counterparts, their density profiles featuring pronounced oscillations. Moreover, the polymer-induced depletion potential between the two walls exhibits an oscillatory profile reminiscent of hard-sphere systems, with oscillations that intensify upon increasing polymer concentration. The obtained form of the depletion interaction is shown to be qualitatively different in comparison to the case of linear polymer solutions at the corresponding densities.