The anomalies and criticality of liquid water

被引:75
作者
Shi, Rui [1 ,2 ]
Tanaka, Hajime [2 ]
机构
[1] Zhejiang Univ, Dept Phys, Hangzhou 310027, Peoples R China
[2] Univ Tokyo, Inst Ind Sci, Dept Fundamental Engn, Tokyo 1538505, Japan
基金
日本学术振兴会;
关键词
water's anomalies; liquid-liquid transition; critical point; dynamical fluctuations; two-state model; SUPERCOOLED WATER; SELF-DIFFUSION; 1ST-ORDER TRANSITION; PRESSURE-DEPENDENCE; DYNAMIC CROSSOVER; CRITICAL-POINT; HIGH-DENSITY; TEMPERATURE; BEHAVIOR; ICE;
D O I
10.1073/pnas.2008426117
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
The origin of water's anomalies has been a matter of long-standing debate. A two-state model, dating back to Rontgen, relies on the dynamical coexistence of two types of local structures-locally favored tetrahedral structure (LFTS) and disordered normal-liquid structure (DNLS)-in liquid water. Phenomenologically, this model not only explains water's thermodynamic anomalies but also can rationalize the existence of a liquid-liquid critical point (LLCP) if there is a cooperative formation of LFTS. We recently found direct evidence for the coexistence of LFTS and DNLS in the experimental structure factor of liquid water. However, the existence of the LLCP and its impact on water's properties has remained elusive, leaving the origin of water's anomalies unclear. Here we propose a unique strategy to locate the LLCP of liquid water. First, we make a comprehensive analysis of a large set of experimental structural, thermodynamic, and dynamic data based on our hierarchical two-state model. This model predicts that the two thermodynamic and dynamical fluctuation maxima lines should cross at the LLCP if it exists, which we confirm by hundred-microsecond simulations for model waters. Based on recent experimental results of the compressibility and diffusivity measurements in the no man's land, we reveal that the two lines cross around 184 K and 173 MPa for real water, suggesting the presence of the LLCP around there. Nevertheless, we find that the criticality is almost negligible in the experimentally accessible region of liquid water because it is too far from the LLCP. Our findings would provide a clue to settle the long-standing debate.
引用
收藏
页码:26591 / 26599
页数:9
相关论文
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