Assembly of clathrates from tetrahedral patchy colloids with narrow patches

Here, we revisit the assembly of colloidal tetrahedral patchy particles. Previous studies have shown that the crystallization of diamond from the fluid phase depends more critically on patch width than on the interaction range: particles with patches narrower than 40° crystallize readily and those with wide patches form disordered glass states. We find that the crystalline structure formed from the fluid also depends on the patch width. Whereas particles with intermediate patches assemble into diamond (random stacking of cubic and hexagonal diamond layers), particles with narrow patches (with width ?20° or less) crystallize frequently into clathrates. Free energy calculations show that clathrates are never (in the pressure-temperature plane) thermodynamically more stable than diamond. The assembly of clathrate structures is thus attributed to kinetic factors that originate from the thermodynamic stabilization of pentagonal rings with respect to hexagonal ones as patches become more directional. These pentagonal rings present in the fluid phase assemble into sII clathrate or into large clusters containing 100 particles and exhibiting icosahedral symmetry. These clusters then grow by interpenetration. Still, the organization of these clusters into extended ordered structures was never observed in the simulations.