Corresponding states for mesostructure and dynamics of supercooled water

被引:41
|
作者
Limmer, David T. [1 ]
Chandler, David [1 ]
机构
[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94702 USA
关键词
HOMOGENEOUS ICE NUCLEATION; LIQUID-LIQUID TRANSITION; GLASS-TRANSITION; COMPUTER-SIMULATION; MOLECULAR-DYNAMICS; AQUEOUS-SOLUTIONS; CONDENSED PHASES; CRITICAL-POINT; SILICON; TRANSFORMATION;
D O I
10.1039/c3fd00076a
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Water famously expands upon freezing, foreshadowed by a negative coefficient of expansion of the liquid at temperatures close to its freezing temperature. These behaviors, and many others, reflect the energetic preference for local tetrahedral arrangements of water molecules and entropic effects that oppose it. Here, we provide theoretical analysis of mesoscopic implications of this competition, both equilibrium and non-equilibrium, including mediation by interfaces. With general scaling arguments bolstered by simulation results, and with reduced units that elucidate corresponding states, we derive a phase diagram for bulk and confined water and water-like materials. For water itself, the corresponding states cover the temperature range of 150 K to 300 K and the pressure range of 1 bar to 2 kbar. In this regime, there are two reversible condensed phases - ice and liquid. Out of equilibrium, there is irreversible polyamorphism, i.e., more than one glass phase, reflecting dynamical arrest of coarsening ice. Temperature-time plots are derived to characterize time scales of the different phases and explain contrasting dynamical behaviors of different water-like systems.
引用
收藏
页码:485 / 498
页数:14
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