Self-Assembly of Model Three- and Four-Patch Colloidal Particles in Two Dimensions

A coarse-grained effective solvent model of two-patch particles is extended to study the self-assembly of three- and four-patch particles to two-dimensional honeycomb and square lattices, respectively. Employing this model, grand canonical ensemble simulations are done to calculate vapor-liquid equilibria and the critical temperatures for patchy particles of various patch widths. The range of stability of the liquid, although very limited compared to isotropic particles, which interact through a longer-range potential, depends on the patch width and on the number of patches. Biased sampling and unbiased simulations are also done to investigate the mechanism of nucleation and crystal growth for honeycomb and square lattices, self-assembled from three- and four-patch particles, respectively. A two-step mechanism governs the nucleation of both lattices. In the first step, the particles form a dense amorphous network, and in the second step, the particles inside the amorphous network reorient to form crystalline nuclei. Barrier heights for the nucleation of honeycomb and square lattices are 7.8