Glassy dynamics, spinodal fluctuations, and the kinetic limit of nucleation in suspensions of colloidal hard rods

Using simulations we identify three dynamic regimes in supersaturated isotropic fluid states of short hard rods: (i) for moderate supersaturations, we observe nucleation of multilayered crystalline clusters; (ii) at higher supersaturation, we find nucleation of small crystallites which arrange into long-lived locally favored structures that get kinetically arrested; and (iii) at even higher supersaturation, the dynamic arrest is due to the conventional cage-trapping glass transition. For longer rods we find that the formation of the (stable) smectic phase out of a supersaturated isotropic state is strongly suppressed by an isotropic-nematic spinodal instability that causes huge spinodal-like orientation fluctuations with nematic clusters diverging in size. Our results show that glassy dynamics and spinodal instabilities set kinetic limits to nucleation in highly supersaturated hard-rod fluids.