Perspective: Crossing the Widom line in no man's land: Experiments, simulations, and the location of the liquid-liquid critical point in supercooled water.

The origin of liquid water's anomalous behavior continues to be a subject of interest and debate. One possible explanation is the liquid-liquid critical point hypothesis, which proposes that supercooled water separates into two distinct liquids at low temperatures and high pressures. According to this hypothesis, liquid water's anomalies can be traced back to the critical point associated with this phase separation. If such a critical point actually exists, it is located in a region of the phase diagram known as No Man's Land (NML), where it is difficult to characterize the liquid using conventional experimental techniques due to rapid crystallization. Recently, however, experimentalists have managed to explore NML near the proposed location of the Widom line (i.e., the Kanno-Angell line), thereby providing valuable information concerning the liquid-liquid critical point hypothesis. In this perspective, we analyze these experimental results, in conjunction with molecular dynamics simulations based on the E3B3 water model and discuss their implications for the validity of the liquid-liquid critical point hypothesis and the possible location of water's second critical point.

• Publication year

  2018

• Venue

  Journal of Chemical Physics

• Publication date

  2018-10-14

• Fields of study

  Medicine, Physics, Chemistry

• Identifiers
  DOI 10.1063/1.5046687PMID 30316289
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

• Thermodynamic and structural anomalies of water nanodroplets

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• Communication: Diffusion constant in supercooled water as the Widom line is crossed in no man's land.

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• Comment on "The putative liquid-liquid transition is a liquid-solid transition in atomistic models of water" [I and II: J. Chem. Phys. 135, 134503 (2011); J. Chem. Phys. 138, 214504 (2013)].

  2018cited by this paper
• Nuclear quantum effects on the liquid-liquid phase transition of a water-like monatomic liquid.

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• Comment on “Maxima in the thermodynamic response and correlation functions of deeply supercooled water”

  2018cited by this paper
• Fragile to strong crossover and Widom line in supercooled water: A comparative study

  2018cited by this paper
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  2018cited by this paper
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