Crystallization of hard-sphere glasses

We study by molecular dynamics the interplay between arrest and crystallization in hard spheres. For state points in the plane of volume fraction ($0.54\le phi\le 0.63$) and polydispersity ($0 \leq s \leq 0.085$), we delineate states that spontaneously crystallize from those that do not. For noncrystallizing (or precrystallization) samples we find isodiffusivity lines consistent with an ideal glass transition at $\phi_g \approx 0.585$,independentof$s$\mathrm{.}Despitethis,for$s<0.05$, crystallization occurs at $\varphi >{\varphi }_g$. This happens on time scales for which the system is aging, and a diffusive regime in the mean square displacement is not reached; by those criteria, the system is a glass. Hence, contrary to a widespread assumption in the colloid literature, the occurrence of spontaneous crystallization within a bulk amorphous state does not prove that this state was an ergodic fluid rather than a glass.