skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Water: A Tale of Two Liquids

Abstract

Water is the most abundant liquid on earth and also the substance with the largest number of anomalies in its properties. It is a prerequisite for life and as such a most important subject of current research in chemical physics and physical chemistry. In spite of its simplicity as a liquid, it has an enormously rich phase diagram where different types of ices, amorphous phases, and anomalies disclose a path that points to unique thermodynamics of its supercooled liquid state that still hides many unraveled secrets. In this review we describe the behavior of water in the regime from ambient conditions to the deeply supercooled region. The review describes simulations and experiments on this anomalous liquid. Several scenarios have been proposed to explain the anomalous properties that become strongly enhanced in the supercooled region. Among those, the second critical-point scenario has been investigated extensively, and at present most experimental evidence point to this scenario. Starting from very low temperatures, a coexistence line between a high-density amorphous phase and a low-density amorphous phase would continue in a coexistence line between a high-density and a low-density liquid phase terminating in a liquid–liquid critical point, LLCP. On approaching this LLCP from the one-phasemore » region, a crossover in thermodynamics and dynamics can be found. This is discussed based on a picture of a temperature-dependent balance between a high-density liquid and a low-density liquid favored by, respectively, entropy and enthalpy, leading to a consistent picture of the thermodynamics of bulk water. Ice nucleation is also discussed, since this is what severely impedes experimental investigation of the vicinity of the proposed LLCP. Experimental investigation of stretched water, i.e., water at negative pressure, gives access to a different regime of the complex water diagram. Different ways to inhibit crystallization through confinement and aqueous solutions are discussed through results from experiments and simulations using the most sophisticated and advanced techniques. These findings represent tiles of a global picture that still needs to be completed. In conclusion, some of the possible experimental lines of research that are essential to complete this picture are explored.« less

Authors:
 [1];  [2];  [3];  [4];  [5];  [6];  [7];  [8];  [9];  [10];  [11];  [7];  [12];  [13];  [14];  [2]
  1. Dipartimento di Matematica e Fisica, Università Roma Tre, Via della Vasca Navale 84, 00146 Rome, Italy
  2. Department of Physics, AlbaNova University Center, Stockholm University, SE-106 91 Stockholm, Sweden
  3. Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287, United States
  4. Institute for Physical Science and Technology and Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, Maryland 20742, United States
  5. Institut Lumière Matière, UMR5306 Université Claude Bernard Lyon 1-CNRS, Université de Lyon, Institut Universitaire de France, 69622 Villeurbanne, France
  6. Department of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016, India
  7. Center for Polymer Studies and Department of Physics, Boston University, Boston, Massachusetts 02215, United States
  8. Institute of Physical Chemistry, University of Innsbruck, 6020 Innsbruck, Austria
  9. Department of Chemical and Biological Engineering, Princeton University, Princeton, New Jersey 08544, United States
  10. Institute of Industrial Science, University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo 153-8505, Japan, School of Mathematics, University of Bristol, Bristol BS8 1TW, United Kingdom
  11. Biomedical and X-ray Physics, Department of Applied Physics, AlbaNova University Center, KTH Royal Institute of Technology, SE-106 91 Stockholm, Sweden
  12. Institute of Industrial Science, University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo 153-8505, Japan
  13. Departamento de Quimica Fisica, Facultad de Ciencias Quimicas, Universidad Complutense de Madrid, 28040 Madrid, Spain
  14. International Centre for Quantum Materials and School of Physics, Peking University, Beijing 100871, China, Collaborative Innovation Center of Quantum Matter, Beijing 100871, China
Publication Date:
Research Org.:
Princeton Univ., NJ (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Swedish Research Council (SRC); European Research Council (ERC); Japan Society for the Promotion of Science (JSPS); National Natural Science Foundation of China (NNSFC)
OSTI Identifier:
1355807
Alternate Identifier(s):
OSTI ID: 1435719
Grant/Contract Number:  
SC0002128; 09-BLAN-0404-01; CHE 12-13265; 21224011; 25000002; 11174006; 11290162; 11525520; 2012CB921404; 2015CB856801
Resource Type:
Published Article
Journal Name:
Chemical Reviews
Additional Journal Information:
Journal Name: Chemical Reviews Journal Volume: 116 Journal Issue: 13; Journal ID: ISSN 0009-2665
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Gallo, Paola, Amann-Winkel, Katrin, Angell, Charles Austen, Anisimov, Mikhail Alexeevich, Caupin, Frédéric, Chakravarty, Charusita, Lascaris, Erik, Loerting, Thomas, Panagiotopoulos, Athanassios Zois, Russo, John, Sellberg, Jonas Alexander, Stanley, Harry Eugene, Tanaka, Hajime, Vega, Carlos, Xu, Limei, and Pettersson, Lars Gunnar Moody. Water: A Tale of Two Liquids. United States: N. p., 2016. Web. doi:10.1021/acs.chemrev.5b00750.
Gallo, Paola, Amann-Winkel, Katrin, Angell, Charles Austen, Anisimov, Mikhail Alexeevich, Caupin, Frédéric, Chakravarty, Charusita, Lascaris, Erik, Loerting, Thomas, Panagiotopoulos, Athanassios Zois, Russo, John, Sellberg, Jonas Alexander, Stanley, Harry Eugene, Tanaka, Hajime, Vega, Carlos, Xu, Limei, & Pettersson, Lars Gunnar Moody. Water: A Tale of Two Liquids. United States. doi:10.1021/acs.chemrev.5b00750.
Gallo, Paola, Amann-Winkel, Katrin, Angell, Charles Austen, Anisimov, Mikhail Alexeevich, Caupin, Frédéric, Chakravarty, Charusita, Lascaris, Erik, Loerting, Thomas, Panagiotopoulos, Athanassios Zois, Russo, John, Sellberg, Jonas Alexander, Stanley, Harry Eugene, Tanaka, Hajime, Vega, Carlos, Xu, Limei, and Pettersson, Lars Gunnar Moody. Wed . "Water: A Tale of Two Liquids". United States. doi:10.1021/acs.chemrev.5b00750.
@article{osti_1355807,
title = {Water: A Tale of Two Liquids},
author = {Gallo, Paola and Amann-Winkel, Katrin and Angell, Charles Austen and Anisimov, Mikhail Alexeevich and Caupin, Frédéric and Chakravarty, Charusita and Lascaris, Erik and Loerting, Thomas and Panagiotopoulos, Athanassios Zois and Russo, John and Sellberg, Jonas Alexander and Stanley, Harry Eugene and Tanaka, Hajime and Vega, Carlos and Xu, Limei and Pettersson, Lars Gunnar Moody},
abstractNote = {Water is the most abundant liquid on earth and also the substance with the largest number of anomalies in its properties. It is a prerequisite for life and as such a most important subject of current research in chemical physics and physical chemistry. In spite of its simplicity as a liquid, it has an enormously rich phase diagram where different types of ices, amorphous phases, and anomalies disclose a path that points to unique thermodynamics of its supercooled liquid state that still hides many unraveled secrets. In this review we describe the behavior of water in the regime from ambient conditions to the deeply supercooled region. The review describes simulations and experiments on this anomalous liquid. Several scenarios have been proposed to explain the anomalous properties that become strongly enhanced in the supercooled region. Among those, the second critical-point scenario has been investigated extensively, and at present most experimental evidence point to this scenario. Starting from very low temperatures, a coexistence line between a high-density amorphous phase and a low-density amorphous phase would continue in a coexistence line between a high-density and a low-density liquid phase terminating in a liquid–liquid critical point, LLCP. On approaching this LLCP from the one-phase region, a crossover in thermodynamics and dynamics can be found. This is discussed based on a picture of a temperature-dependent balance between a high-density liquid and a low-density liquid favored by, respectively, entropy and enthalpy, leading to a consistent picture of the thermodynamics of bulk water. Ice nucleation is also discussed, since this is what severely impedes experimental investigation of the vicinity of the proposed LLCP. Experimental investigation of stretched water, i.e., water at negative pressure, gives access to a different regime of the complex water diagram. Different ways to inhibit crystallization through confinement and aqueous solutions are discussed through results from experiments and simulations using the most sophisticated and advanced techniques. These findings represent tiles of a global picture that still needs to be completed. In conclusion, some of the possible experimental lines of research that are essential to complete this picture are explored.},
doi = {10.1021/acs.chemrev.5b00750},
journal = {Chemical Reviews},
number = 13,
volume = 116,
place = {United States},
year = {2016},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/acs.chemrev.5b00750

Citation Metrics:
Cited by: 81 works
Citation information provided by
Web of Science

Save / Share:

Works referencing / citing this record:

Self-diffusion coefficient of bulk and confined water: a critical review of classical molecular simulation studies
journal, August 2018

  • Tsimpanogiannis, Ioannis N.; Moultos, Othonas A.; Franco, Luís F. M.
  • Molecular Simulation, Vol. 45, Issue 4-5
  • DOI: 10.1080/08927022.2018.1511903

Effect of truncating electrostatic interactions on predicting thermodynamic properties of water–methanol systems
journal, August 2018


Evaporating laminar microjets for studies of rapidly evolving structural transformations in supercooled liquids
journal, January 2018


Soft condensed matter physics of foods and macronutrients
journal, July 2019


Streams, cascades, and pools: various water cluster motifs in structurally similar Ni( ii ) complexes
journal, January 2018

  • Saraei, Nina; Hietsoi, Oleksandr; Mullins, Christopher S.
  • CrystEngComm, Vol. 20, Issue 44
  • DOI: 10.1039/c8ce01153b

Communication: Diffusion constant in supercooled water as the Widom line is crossed in no man’s land
journal, May 2018

  • Ni, Yicun; Hestand, Nicholas J.; Skinner, J. L.
  • The Journal of Chemical Physics, Vol. 148, Issue 19
  • DOI: 10.1063/1.5029822

Soft condensed matter physics of foods and macronutrients
journal, July 2019


Streams, cascades, and pools: various water cluster motifs in structurally similar Ni( ii ) complexes
journal, January 2018

  • Saraei, Nina; Hietsoi, Oleksandr; Mullins, Christopher S.
  • CrystEngComm, Vol. 20, Issue 44
  • DOI: 10.1039/c8ce01153b

Effect of solute nature on the polyamorphic transition in glassy polyol aqueous solutions
journal, August 2017

  • Suzuki, Yoshiharu
  • The Journal of Chemical Physics, Vol. 147, Issue 6
  • DOI: 10.1063/1.4998201

Communication: Diffusion constant in supercooled water as the Widom line is crossed in no man’s land
journal, May 2018

  • Ni, Yicun; Hestand, Nicholas J.; Skinner, J. L.
  • The Journal of Chemical Physics, Vol. 148, Issue 19
  • DOI: 10.1063/1.5029822

Experimental estimation of the location of liquid-liquid critical point for polyol aqueous solutions
journal, November 2018

  • Suzuki, Yoshiharu
  • The Journal of Chemical Physics, Vol. 149, Issue 20
  • DOI: 10.1063/1.5050832

Self-diffusion coefficient of bulk and confined water: a critical review of classical molecular simulation studies
journal, August 2018

  • Tsimpanogiannis, Ioannis N.; Moultos, Othonas A.; Franco, Luís F. M.
  • Molecular Simulation, Vol. 45, Issue 4-5
  • DOI: 10.1080/08927022.2018.1511903

Effect of truncating electrostatic interactions on predicting thermodynamic properties of water–methanol systems
journal, August 2018


Evaporating laminar microjets for studies of rapidly evolving structural transformations in supercooled liquids
journal, January 2018


Thermodynamics of Fluid Polyamorphism
journal, January 2018