Revealing the role of liquid preordering in crystallisation of supercooled liquids

YC Hu and H Tanaka, NATURE COMMUNICATIONS, 13, 4519 (2022).

DOI: 10.1038/s41467-022-32241-z

The recent discovery of non-classical crystal nucleation pathways has revealed the role of fluctuations in the liquid structural order, not considered in classical nucleation theory. On the other hand, classical crystal growth theory states that crystal growth is independent of interfacial energy, but this is questionable. Here we elucidate the role of liquid structural ordering in crystal nucleation and growth using computer simulations of supercooled liquids. We find that suppressing the crystal-like structural order in the supercooled liquid through a new order-killing strategy can reduce the crystallisation rate by several orders of magnitude. This indicates that crystal-like liquid preordering and the associated interfacial energy reduction play an essential role in nucleation and growth processes, forcing critical modifications of the classical crystal growth theory. Furthermore, we evaluate the importance of this additional factor for different types of liquids. These findings shed new light on the fundamental understanding of crystal growth kinetics. In classical nucleation theory, structural order in the liquid phase is not considered. But simulations of supercooled liquids now show that crystal-like liquid preordering play an essential role in nucleation and growth processes - calling for extensions of the classical theory.

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