Self-Assembly and Phase Behavior of Janus Rods: Competition Between Shape and Potential Anisotropy

Abstract

We characterize the self-assembly and phase behavior of Janus rods over a broad range of temperatures and volume fractions, using Langevin dynamics simulations and free energy calculations. The Janus rods consist of a line of fused overlapping spheres that interact via a soft-core repulsive potential, with the addition of an attractive pseudo-square-well tail to a fraction of the spheres (the coverage) ranging from 5\% to 100\% of sites. Competition between the stability of liquid crystal phases originating from shape anisotropy and assembly driven by directional interactions gives rise to a rich polymorphism that depends on the coverage. At low density near the Boyle temperature, we observe the formation of spherical and tubular micelles at low coverage, while at higher coverage randomly oriented monolayers form as the attractive parts of the rods overlap. At higher density, bilayer structures appear and merge to form smectic and crystalline lamellar phases. All of these structures gradually become unstable as the temperature is increased until eventually regular nematic and smectic phases appear, consistent with the hard rod limit. Our results indicate that the intermediate regime where shape-entropic effects compete with anisotropic attractions provided by site specificity is rich in structural possibilities, and should help guide the design of rod-like colloids for specific applications.