Structural transformation in supercooled water controls the crystallization rate of ice

TL;DR

This study uses coarse-grained simulations to link the structural changes in supercooled water to its thermodynamic anomalies and the rate of ice crystallization, revealing a maximum crystallization rate near 225 K.

Contribution

It demonstrates that a sharp increase in four-coordinated molecules in supercooled water controls its thermodynamics and crystallization mechanism, providing a microscopic understanding of water's nucleation behavior.

Findings

Crystallization rate peaks around 225 K.

Structural transformation involves increased four-coordinated molecules.

Liquid water's metastability limit is just below 225 K.

Abstract

One of water's unsolved puzzles is the question of what determines the lowest temperature to which it can be cooled before freezing to ice. The supercooled liquid has been probed experimentally to near the homogeneous nucleation temperature TH{\approx}232 K, yet the mechanism of ice crystallization - including the size and structure of critical nuclei - has not yet been resolved. The heat capacity and compressibility of liquid water anomalously increase upon moving into the supercooled region according to a power law that would diverge at Ts{\approx}225 K,(1,2) so there may be a link between water's thermodynamic anomalies and the crystallization rate of ice. But probing this link is challenging because fast crystallization prevents experimental studies of the liquid below TH. And while atomistic studies have captured water crystallization(3), the computational costs involved have so far prevented an assessment of the rates and mechanism involved. Here we report coarse-grained molecular simulations with the mW water model(4) in the supercooled regime around TH, which reveal that a sharp increase in the fraction of four-coordinated molecules in supercooled liquid water explains its anomalous thermodynamics and also controls the rate and mechanism of ice formation. The simulations reveal that the crystallization rate of water reaches a maximum around 225 K, below which ice nuclei form faster than liquid water can equilibrate. This implies a lower limit of metastability of liquid water just below TH and well above its glass transition temperature Tg{\approx}136 K. By providing a relationship between the structural transformation in liquid water, its anomalous thermodynamics and its crystallization rate, this work provides a microscopic foundation to the experimental finding that the thermodynamics of water determines the rates of homogeneous nucleation of ice.(5)