Conformational behavior and self-assembly of disjoint semi-flexible ring polymers adsorbed on solid substrates

Abstract

The conformational behavior and spatial organization of self-avoiding semi-flexible ring polymers, that are fully adsorbed on solid substrates, are investigated via systematic coarse-grained molecular dynamics simulations. Our results show that both conformations and spatial organization of the polymers depend strongly on their bending stiffness, κ, and on their areal number density, ρ. For ρ < ρ*, where ρ* is the overlap density, and for low values of κ, thermal fluctuations lead to weakly anisotropic instantaneous conformations of the polymers. The interplay between thermal fluctuations and polymer stiffness leads to a non-monotonic dependence of the polymers elongation on κ with a maximum elongation at some intermediate κ. Regardless of κ, the polymers elongation is almost independent of ρ for ρ ≲ ρ*, then increases with ρ. At ρ ≈ ρ* and high κ, the almost circularly-shaped polymers self-assemble into a triangular lattice with quasi-long range order. For ρ above ρ* and high κ, crowding of the polymers leads to their self-assembly into liquid-crystalline phases. In particular, for ρ moderately above ρ* and high κ, the polymer conformations are obround and self-assemble into domains with smectic-A-like order. At higher densities, the polymer have a biconcave geometry and self-assemble into domains with smectic-C-like order.