Assembly of trivalent particles under confinement: from an exotic solid phase to a liquid phase at low temperature

Abstract

Using computer simulations, we study the phase diagram of a two-dimensional system of disk particles with three patches distributed symmetrically along the particle equator. The geometry of the particles is compatible with a honey-comb lattice at moderately low temperature and pressure, whereas it is expected that the system forms a close-packed triangular lattice at high temperature and pressure. The effect of patch size within the single bond per patch regime was investigated, and it was found that the topology of the phase diagram changes drastically with patch size. Interestingly, in particles with small patches (with a half opening angle of 10°), the fluid transforms upon increasing the pressure into a rather exotic phase that can be understood as a honey-comb lattice whose voids are filled continuously with additional particles that remain, on average, unbound. Eventually, all the voids are occupied so that particles are located at the positions of a triangular lattice, but only two thirds of the particles are orientationally ordered whereas the remaining one third can rotate almost freely as in a plastic crystal. At moderately low temperature, the fluid transforms into a nearly empty honey-comb lattice, whereas at high temperature it transforms directly into the almost filled lattice. Interestingly, for particles with big patches (with a half opening angle of 20°), the honey-comb and triangular lattices are separated by a liquid phase that remains stable down to fairly low temperatures. Less surprisingly, only particles with big patches exhibit an equilibrium gas–liquid separation.