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

被引:144
作者
Xu, Yuntao [1 ]
Petrik, Nikolay G. [1 ]
Smith, R. Scott [1 ]
Kay, Bruce D. [1 ]
Kimmel, Greg A. [1 ]
机构
[1] Pacific Northwest Natl Lab, Phys & Computat Sci Directorate, Div Phys Sci, Chem Phys & Anal, Richland, WA 99352 USA
关键词
supercooled water; self-diffusion; crystallization kinetics; dynamic crossover; STOKES-EINSTEIN RELATION; SELF-DIFFUSION; LIQUID WATER; TEMPERATURE-DEPENDENCE; MOLECULAR-BEAMS; LIMITED GROWTH; WIDOM LINE; KINETICS; GLASS; TRANSITION;
D O I
10.1073/pnas.1611395114
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
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.
引用
收藏
页码:14921 / 14925
页数:5
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