Crystallization is one of the most fundamental nonequilibrium phenomena universal to a variety of materials. It has so far been assumed that a supercooled liquid is in a “homogeneous disordered state” before crystallization. Contrary to this common belief, we reveal that a supercooled colloidal liquid is actually not homogeneous, but has transient medium-range structural order. We find that nucleation preferentially takes place in regions of high structural order via wetting effects, which reduce the crystal–liquid interfacial energy significantly and thus promotes crystal nucleation. This novel scenario provides a clue to solving a long-standing mystery concerning a large discrepancy between the rigorous numerical estimation of the nucleation rate on the basis of the classical nucleation theory and the experimentally observed ones. Our finding may shed light not only on the mechanism of crystal nucleation, but also on the fundamental nature of a supercooled liquid state.

A glassy state of matter results if crystallization is avoided upon cooling or increasing density. However, the physical factors controlling the ease of vitrification and nature of the glass transition remain elusive. Using numerical simulations of polydisperse hard disks, we find a direct relation between medium-range crystalline ordering and the slow dynamics which characterizes the glass transition. This suggests an intriguing scenario that the strength of frustration controls both the ease of vitrification and nature of the glass transition. Vitrification may be a process of hidden crystalline ordering under frustration, at least in our system.