Nanosecond Freezing of Water at High Pressures: Nucleation and Growth near the Metastability Limit

The fundamental study of phase transition kinetics has motivated experimental methods toward achieving the largest degree of undercooling possible, more recently culminating in the technique of rapid, quasi-isentropic compression. This approach has been demonstrated to freeze water into the high-pressure ice VII phase on nanosecond timescales, with some experiments undergoing heterogeneous nucleation while others, in apparent contradiction, suggest a homogeneous nucleation mode. In this study, we show through a combination of theory, simulation, and analysis of experiments that these seemingly contradictory results are in agreement when viewed from the perspective of classical nucleation theory. We find that, perhaps surprisingly, classical nucleation theory is capable of accurately predicting the solidification kinetics of ice VII formation under an extremely high driving force (vertical bar Delta mu/k(B)T vertical bar approximate to 1) but only if amended by two important considerations: (i) transient nucleation and (ii) separate liquid and solid temperatures. This is the first demonstration of a model that is able to reproduce the experimentally observed rapid freezing kinetics.