Hard spheres: crystallization and glass formation

Motivated by old experiments on colloidal suspensions, we report molecular dynamics simulations of assemblies of hard spheres, addressing crystallization and glass formation. The simulations cover wide ranges of polydispersity s (standard deviation of the particle size distribution divided by its mean) and particle concentration. No crystallization is observed for s > 0.07. For 0.02 < s < 0.07, we find that increasing the polydispersity at a given concentration slows down crystal nucleation. The main effect here is that polydispersity reduces the supersaturation since it tends to stabilize the fluid but to destabilize the crystal. At a given polydispersity (< 0.07), we find three regimes of nucleation: standard nucleation and growth at concentrations in and slightly above the coexistence region; 'spinodal nucleation', where the free-energy barrier to nucleation appears to be negligible, at intermediate concentrations; and, at the highest concentrations, a new mechanism, still to be fully understood, which only requires small rearrangement of the particle positions. The cross-over between the second and third regimes occurs at a concentration, approximately 58 per cent by volume, where the colloid experiments show a marked change in the nature of the crystals formed and the particle dynamics indicate an 'ideal' glass transition.