Journal Article

Structural transformation in supercooled water controls the crystallization rate of ice

Molinero, Valeria, Moore, Emily B.

2011

Overview

How water forms ice The various anomalous properties of water have puzzled scientists for decades, and many hypotheses have been put forward to explain their origin. One mystery is the question of what determines the lowest temperature to which water can be cooled before it freezes to ice. Rapid crystallization at low temperatures hampers experimental studies, and simulations are usually prohibitively costly in terms of computer time. Using a simple water model that allows demanding calculations, Emily Moore and Valeria Molinero now show that a sharp increase in the fraction of four-coordinated molecules in supercooled liquid water controls the rate and mechanism of ice formation. The structural change also results in a peak in the rate of crystallization at 225 K; below this temperature, ice nuclei form faster than liquid water can equilibrate. This finding explains the observed thermodynamic anomalies, and why homogeneous ice nucleation rates depend on the thermodynamics of water. 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, T H  ≈ 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 on moving into the supercooled region, according to power laws that would diverge (that is, approach infinity) at ∼225 K (refs 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 T H . And although atomistic studies have captured water crystallization 3 , high computational costs 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 T H 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 mechanisms of ice formation. The results of the simulations and classical nucleation theory using experimental data suggest 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 T H and well above its glass transition temperature, 136 K. By establishing a relationship between the structural transformation in liquid water and its anomalous thermodynamics and crystallization rate, our findings also provide mechanistic insight into the observed 5 dependence of homogeneous ice nucleation rates on the thermodynamics of water.

• Publisher: Nature Publishing Group UK,Nature Publishing Group
• Subject: 639/301/119 / 639/638/440/951 / 704/106 / Computer simulation / Condensed matter: structure, mechanical and thermal properties / Cooling / Crystallization / Equations of state, phase equilibria, and phase transitions / Exact sciences and technology / Freezing / Humanities and Social Sciences / Ice / Ice formation / letter / Links / Liquids / multidisciplinary / Nucleation / Physics / Properties / Science / Science (multidisciplinary) / Solid-liquid transitions / Specific phase transitions / Structure / Studies / Supercooled liquids / Temperature / Thermal properties / Thermodynamics / Transformations / Transition temperatures / Water