Anomalous Behavior of the Homogeneous Ice Nucleation Rate in “No-Man’s Land”

We present an analysis of ice nucleation kinetics from near-ambient pressure water as temperature decreases below the homogeneous limit <i>T</i>_H by cooling micrometer-sized droplets (microdroplets) evaporatively at 10³–10⁴ K/s and probing the structure ultrafast using femtosecond pulses from the Linac Coherent Light Source (LCLS) free-electron X-ray laser. Below 232 K, we observed a slower nucleation rate increase with decreasing temperature than anticipated from previous measurements, which we suggest is due to the rapid decrease in water’s diffusivity. This is consistent with earlier findings that microdroplets do not crystallize at <227 K, but vitrify at cooling rates of 10⁶–10⁷ K/s. We also hypothesize that the slower increase in the nucleation rate is connected with the proposed “fragile-to-strong” transition anomaly in water