The microscopic pathway to crystallization in supercooled liquids

Abstract: Despite its fundamental and technological importance, a microscopic understanding of the crystallization process is still elusive. By computer simulations of the hard-sphere model we reveal the mechanism by which thermal fluctuations drive the transition from the supercooled liquid state to the crystal state. In particular we show that fluctuations in bond orientational order trigger the nucleation process, contrary to the common belief that the transition is initiated by density fluctuations. Moreover, the analysis of bond orientational fluctuations shows that these not only act as seeds of the nucleation process, but also i) determine the particular polymorph which is to be nucleated from them and ii) at high density favour the formation of fivefold structures which can frustrate the formation of crystals. These results can shed new light on our understanding of the relationship between crystallization and vitrification.