4.8 Article

Growth rate of crystalline ice and the diffusivity of supercooled water from 126 to 262 K

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NATL ACAD SCIENCES
DOI: 10.1073/pnas.1611395114

关键词

supercooled water; self-diffusion; crystallization kinetics; dynamic crossover

资金

  1. US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences
  2. Department of Energy's Office of Biological and Environmental Research

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Understanding deeply supercooled water is key to unraveling many of water's anomalous properties. However, developing this understanding has proven difficult due to rapid and uncontrolled crystallization. Using a pulsed-laser-heating technique, we measure the growth rate of crystalline ice, G(T), for 180 K < T < 262 K, that is, deep within water's no man's land in ultrahigh-vacuum conditions. Isothermal measurements of G(T) are also made for 126 K <= T <= 151 K. The self-diffusion of supercooled liquid water, D(T), is obtained from G(T) using the Wilson-Frenkel model of crystal growth. For T > 237 K and P similar to 10(-8) Pa, G(T) and D(T) have super-Arrhenius (fragile) temperature dependences, but both cross over to Arrhenius (strong) behavior with a large activation energy in no man's land. The fact that G(T) and D(T) are smoothly varying rules out the hypothesis that liquid water's properties have a singularity at or near 228 K at ambient pressures. However, the results are consistent with a previous prediction for D(T) that assumed no thermodynamic transitions occur in no man's land.

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