Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

Decompression-induced melting of ice IV and the liquid–liquid transition in water

Nature volume 392, pages 164–168 (1998)Cite this article

Abstract

Although liquid water has been the focus of intensive research for over 100 years, a coherent physical picture that unifies all of the known anomalies of this liquid1,2,3, is still lacking. Some of these anomalies occur in the supercooled region, and have been rationalized on the grounds of a possible retracing of the liquid–gas spinodal (metastability limit) line into the supercooled liquid region4,5,6,7, or alternatively the presence of a line of first-order liquid–liquid phase transitions in this region which ends in a critical point8,9,10,11,12,13,14,. But these ideas remain untested experimentally, in part because supercooled water can be probed only above the homogeneous nucleation temperature TH at which water spontaneously crystallizes. Here we report an experimental approach that is not restricted by the barrier imposed by TH, involving measurement of the decompression-induced melting curves of several high-pressure phases of ice in small emulsified droplets. We find that the melting curve for ice IV seems to undergo a discontinuity at precisely the location proposed for the line of liquid–liquid phase transitions8. This is consistent with, but does not prove, the coexistence of two different phases of (supercooled) liquid water. From the experimental data we calculate a possible Gibbs potential surface and a corresponding equation of state for water, from the forms of which we estimate the coordinates of the liquid–liquid critical point to be at pressure Pc ≈ 0.1 GPa and temperature Tc ≈ 220 K.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Overall logic of the present experiment.
Figure 2: Data obtained in the present experiment.
Figure 3: Gibbs potential surface for liquid water probed in the present experiments for both its stable and metastable regions.
Figure 4: Application of data obtained in the present experiment to reconstruct the Gibbs potential surface and the thermodynamic equation of state V = V(P, T).

Similar content being viewed by others

References

  1. Debenedetti, P. G. Metastable Liquids (Princeton Univ. Press, (1997)).

    Google Scholar 

  2. Angell, C. A. Formation of glasses from liquids and biopolymers. Science 267, 1924–1935 (1995).

    Article  ADS  CAS  Google Scholar 

  3. Fourkas, J. T., Kivelson, D., Mohanty, U. & Nelson, K. A. (eds) Supercooled Liquids: Advances and Novel Applications (ACS Books, Washington DC, (1997)).

    Book  Google Scholar 

  4. Speedy, R. J. & Angell, C. A. Isothermal compressibility of supercooled water and evidence for a thermodynamic singularity at −45 C. J. Chem. Phys. 65, 851–858 (1976).

    Article  ADS  CAS  Google Scholar 

  5. Speedy, R. J. Stability-limit conjecture. An interpretation of the properties of water. J. Phys. Chem. 86, 982–991 (1982).

    Article  CAS  Google Scholar 

  6. Borick, S. S. & Debenedetti, P. G. Equilibrium, stability and density anomalies in a lattice model with core softening and directional bonding. J. Phys. Chem. 97, 6292–6303 (1993).

    Article  CAS  Google Scholar 

  7. Borick, S. S., Debenedetti, P. G. & Sastry, S. Alattice model of network-forming fluids with orientation-dependent bonding: equilibrium, stability, and implications from the phase behavior of supercooled water. J. Phys. Chem. 99, 3781–3793 (1995).

    Article  CAS  Google Scholar 

  8. Poole, P. H., Sciortino, F., Essmann, U. & Stanley, H. E. Phase behaviour of metastable water. Nature 360, 324–328 (1992).

    Article  ADS  CAS  Google Scholar 

  9. Tanaka, H. Aself-consistent phase diagram for supercooled water. Nature 380, 328–331 (1996).

    Article  ADS  CAS  Google Scholar 

  10. Tanaka, H. Phase behaviors of supercooled water: reconciling a critical point of amorphous ices with spinodal instability. J. Chem. Phys. 105, 5099–5111 (1996).

    Article  ADS  CAS  Google Scholar 

  11. Roberts, C. J., Panagiotopoulos, A. Z. & Debenedetti, P. G. Liquid-liquid immiscibility in pure fluids: polyamorphism in simulations of a network-forming fluid. Phys. Rev. Lett. 77, 4386–4389 (1996).

    Article  ADS  CAS  Google Scholar 

  12. Roberts, C. J. & Debenedetti, P. G. Polyamorphism and density anomalies in network-forming fluids: zeroth- and first-order approximations. J. Chem. Phys. 105, 658–672 (1996).

    Article  ADS  CAS  Google Scholar 

  13. Harrington, S., Zhang, R., Poole, P. H., Sciortino, F. & Stanley, H. E. Liquid-liquid phase transition: Evidence from simulations. Phys. Rev. Lett. 78, 2409–2412 (1997).

    Article  ADS  CAS  Google Scholar 

  14. Sciortino, F., Poole, P. H., Essmann, U. & Stanley, H. E. Line of compressibility maxima in the phase diagram of supercooled water. Phys. Rev. E 55, 727–737 (1997).

    Article  ADS  CAS  Google Scholar 

  15. Mishima, O., Calvert, L. D. & Whalley, E. An apparently first-order transition between two amorphous phases of ice induced by pressure. Nature 314, 76–78 (1985).

    Article  ADS  CAS  Google Scholar 

  16. Mishima, O. Relationship between melting and amorphization of ice. Nature 384, 546–549 (1996).

    Article  ADS  CAS  Google Scholar 

  17. Bridgman, P. W. Water, in the liquid and five solid forms, under pressure. Proc. Am. Acad. Arts Sci. 47, 441–558 (1911).

    Article  CAS  Google Scholar 

  18. Evans, L. F. Selective nucleation of the high pressure ices. J. Appl. Phys. 38, 4930–4932 (1967).

    Article  ADS  CAS  Google Scholar 

  19. Kanno, H., Speedy, R. & Angell, C. A. Supercooling of water to −92 °C under pressure. Science 189, 880–881 (1975).

    Article  ADS  CAS  Google Scholar 

  20. Whalley, E., Klug, D. D. & Handa, Y. P. Entropy of amorphous ice. Nature 342, 782–783 (1989).

    Article  ADS  CAS  Google Scholar 

  21. Mishima, O. Reversible first-order transition between two water amorphs at ∼0.2 GPa and ∼135 K. J. Chem. Phys. 100, 5910–5912 (1994).

    Article  ADS  CAS  Google Scholar 

  22. Sastry, S., Debenedetti, P., Sciortino, F. & Stanley, H. E. Singularity-free interpretation of the thermodynamics of supercooled water. Phys. Rev. E 53, 6144–6154 (1996).

    Article  ADS  CAS  Google Scholar 

  23. Fletcher, N. H. The Chemical Physics of Ice (Cambridge Univ. Press, (1970)).

    Book  Google Scholar 

  24. Kamb, B. Structure of ice VI. Science 150, 205–209 (1965).

    Article  ADS  CAS  Google Scholar 

  25. Speedy, R. J. Thermodynamic properties of supercooled water at 1 atm. J. Phys. Chem. 91, 3354–3358 (1987).

    Article  CAS  Google Scholar 

  26. Johari, G. P., Fleissner, G., Hallbrucker, A. & Mayer, E. Thermodynamic continuity between glassy and normal water. J. Phys. Chem. 98, 4719–4725 (1994).

    Article  CAS  Google Scholar 

  27. Bellissent-Funel M. C. & Bosio, L. Aneutron scattering study of liquid D2O. J. Chem. Phys. 102, 3727–3735 (1995).

    Article  ADS  Google Scholar 

  28. Lang, E. & Ludemann, H.-D. Pressure and temperature dependence of the longitudinal deuterium relaxation times in supercooled heavy water to 300 MPa and 188 K. Ber. Bunsenges. Phys. Chem. 84, 462–470 (1980).

    Article  CAS  Google Scholar 

  29. Bridgman, P. W. The pressure-volume-temperature relations of the liquid, and the phase diagram of heavy water. J. Chem. Phys. 3, 597–605 (1935).

    Article  ADS  CAS  Google Scholar 

  30. Speedy, R. J., Debenedetti, P. G., Smith, R. S., Huang, C. & Kay, B. D. The evaporation rate, free energy, and entropy of amorphous water at 150K. J. Chem. Phys. 105, 240–244 (1996).

    Article  ADS  CAS  Google Scholar 

  31. Bruggeller, P. & Mayer, E. Complete vitrification in pure liquid water and diute aqueous solutions. Nature 288, 569–571 (1980).

    Article  ADS  Google Scholar 

  32. Bellissent-Funel, M. C., Bosio, L., Hallbrucker, A., Mayer, E. & Sridi-Dorbez, R. X-ray and neutron scattering studies of the structure of hyperquenched glassy water. J. Chem. Phys. 97, 1282–1286 (1992).

    Article  ADS  CAS  Google Scholar 

  33. Haar, L., Gallagher, J. S. & Kell, G. S. NBS/NRC Steam Tables (Hemisphere, Washington DC, (1984)).

    Google Scholar 

Download references

Acknowledgements

We thank C. A. Angell, K. Aoki, M.-C. Bellissent-Funel, M. Canpolat, H.-D. Lüdemann, P. H. Poole, R. Sadr-Lahijany, S. Sastry, F. Sciortino, F. W. Starr and Y. Suzuki for discussions and reading of manuscript drafts. We also thank C. A. Angell for pointing out subtle ponts that we initially glossed over. This work was supported by CREST (Core Research for Evolutional Science and Technology) of Japan Science and Technology Corporation (JST), BP and the US NSF.

Author information

Authors and Affiliations

  1. National Institute for Research in Inorganic Materials, 305-0044, Japan

    Osamu Mishima

  2. Center for Polymer Studies and Department of Physics, Boston University, Boston, 02215, Massachusetts, USA

    H. Eugene Stanley

Authors
  1. Osamu Mishima
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. H. Eugene Stanley
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Osamu Mishima.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Mishima, O., Stanley, H. Decompression-induced melting of ice IV and the liquid–liquid transition in water. Nature 392, 164–168 (1998). https://doi.org/10.1038/32386

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1038/32386

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing