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Absence of amorphous forms when ice is compressed at low temperature


Amorphous water ice comes in at least three distinct structural forms, all lacking long-range crystalline order. High-density amorphous ice (HDA) was first produced by compressing ice I to 11 kilobar at temperatures below 130 kelvin, and the process was described as thermodynamic melting1, implying that HDA is a glassy state of water. This concept, and the ability to transform HDA reversibly into low-density amorphous ice, inspired the two-liquid water model, which relates the amorphous phases to two liquid waters in the deeply supercooled regime (below 228 kelvin) to explain many of the anomalies of water2 (such as density and heat capacity anomalies). However, HDA formation has also been ascribed3 to a mechanical instability causing structural collapse and associated with kinetics too sluggish for recrystallization to occur. This interpretation is supported by simulations3, analogy with a structurally similar system4, and the observation of lattice-vibration softening as ice is compressed5,6. It also agrees with recent observations of ice compression at higher temperatures—in the ‘no man’s land’ regime, between 145 and 200 kelvin, where kinetics are faster—resulting in crystalline phases7,8. Here we further probe the role of kinetics and show that, if carried out slowly, compression of ice I even at 100 kelvin (a region in which HDA typically forms) gives proton-ordered, but non-interpenetrating, ice IX′, then proton-ordered and interpenetrating ice XV′, and finally ice VIII′. By contrast, fast compression yields HDA but no ice IX, and direct transformation of ice I to ice XV′ is structurally inhibited. These observations suggest that HDA formation is a consequence of a kinetically arrested transformation between low-density ice I and high-density ice XV′ and challenge theories that connect amorphous ice to supercooled liquid water.

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The data that support the findings shown in the figures are available from the corresponding author upon reasonable request.

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  1. 1.

    Mishima, O., Calvert, L. D. & Whalley, E. ‘Melting ice’ I at 77 K and 10 kbar: a new method of making amorphous solids. Nature 310, 393–395 (1984).

  2. 2.

    Gallo, P. et al. Water: a tale of two liquids. Chem. Rev. 116, 7463–7500 (2016).

  3. 3.

    Tse, J. et al. The mechanisms for pressure-induced amorphization of ice Ih. Nature 400, 647–649 (1999).

  4. 4.

    Shephard, J. J. et al. Is high-density amorphous ice simply a “derailed” state along the ice I to ice IV pathway? J. Phys. Chem. Lett. 8, 1645–1650 (2017).

  5. 5.

    Strässle, T., Saitta, A. M., Klotz, S. & Braden, M. Phonon dispersion of ice under pressure. Phys. Rev. Lett. 93, 225901 (2004).

  6. 6.

    Strässle, T., Klotz, S., Hamel, G., Koza, M. M. & Schober, H. Experimental evidence for a crossover between two distinct mechanisms of amorphization in ice Ih under pressure. Phys. Rev. Lett. 99, 175501 (2007).

  7. 7.

    Wang, Y., Zhang, H., Yang, X., Jiang, S. & Goncharov, A. F. Kinetic boundaries and phase transformations of ice I at high pressure. J. Chem. Phys. 148, 044508 (2018).

  8. 8.

    Lin, C. L. et al. Kinetically controlled two-step amorphization and amorphous-amorphous transition in ice. Phys. Rev. Lett. 119, 135701 (2017).

  9. 9.

    Johari, G. P. Liquid state of low-density pressure-amorphized ice above its T g. J. Phys. Chem. B 102, 4711–4714 (1998).

  10. 10.

    Seidl, M. et al. Volumetric study consistent with a glass-to-liquid transition in amorphous ices under pressure. Phys. Rev. B 83, 100201 (2011).

  11. 11.

    Elsaesser, M. S., Winkel, K., Mayer, E. & Loerting, T. Reversibility and isotope effect of the calorimetric glass → liquid transition of low-density amorphous ice. Phys. Chem. Chem. Phys. 12, 708–712 (2010).

  12. 12.

    Giovambattista, N., Angell, C. A., Sciortino, F. & Stanley, H. E. Glass-transition temperature of water: a simulation study. Phys. Rev. Lett. 93, 047801 (2004).

  13. 13.

    Lin, C. L., Smith, J. S., Liu, X. Q., Tse, J. S. & Yang, W. G. Venture into water’s no man’s land: structural transformations of solid H2O under rapid compression and decompression. Phys. Rev. Lett. 121, 225703 (2018).

  14. 14.

    Finney, J. L. et al. Structure of a new dense amorphous ice. Phys. Rev. Lett. 89, 205503 (2002).

  15. 15.

    Tulk, C. A., Hart, R., Klug, D. D., Benmore, C. J. & Neuefeind, J. Adding a length scale to the polyamorphic ice debate. Phys. Rev. Lett. 97, 115503 (2006).

  16. 16.

    Nelmes, R. J. et al. Annealed high-density amorphous ice under pressure. Nat. Phys. 2, 414–418 (2006).

  17. 17.

    Kohl, I., Mayer, E. & Hallbrucker, A. Ice XII forms on compression of hexagonal ice at 77 K via high-density amorphous water. Phys. Chem. Chem. Phys. 3, 602–605 (2001).

  18. 18.

    Salzmann, C. G., Loerting, T., Kohl, I., Mayer, E. & Hallbrucker, A. Pure ice IV from high-density amorphous ice. J. Phys. Chem. B 106, 5587–5590 (2002).

  19. 19.

    Salzmann, C. G., Radaelli, P. G., Hallbrucker, A., Mayer, E. & Finney, J. L. The preparation and structures of hydrogen ordered phases of ice. Science 311, 1758–1761 (2006).

  20. 20.

    Salzmann, C. G. et al. Detailed crystallographic analysis of the ice VI to ice XV hydrogen ordering phase transition. J. Chem. Phys. 145, (2016).

  21. 21.

    Klotz, S., Hamel, G., Loveday, J. S., Nelmes, R. J. & Guthrie, M. Recrystallisation of HDA ice under pressure by in-situ neutron diffraction to 3.9 GPa. Z. Kristallogr. 218, 117–122 (2003).

  22. 22.

    Hallbrucker, A., Mayer, E. & Johari, G. P. Glass-transition in pressure-amorphized hexagonal ice: a comparison with amorphous forms made from the vapor and liquid. J. Phys. Chem. 93, 7751–7752 (1989).

  23. 23.

    Tse, J. S. & Klug, D. D. Pressure amorphized ices – an atomistic perspective. Phys. Chem. Chem. Phys. 14, 8255–8263 (2012).

  24. 24.

    Tse, J. S. & Klein, M. L. Pressure-induced amorphization of ice Ih. J. Chem. Phys. 92, 3992–3994 (1990).

  25. 25.

    Limmer, D. T. & Chandler, D. Theory of amorphous ices. Proc. Natl Acad. Sci. USA 111, 9413–9418 (2014).

  26. 26.

    Limmer, D. T. & Chandler, D. Comment on “Spontaneous liquid-liquid phase separation of water”. Phys. Rev. E 91, 016301 (2015).

  27. 27.

    English, N. J. & Tse, J. S. Massively parallel molecular dynamics simulation of formation of ice-crystallite precursors in supercooled water: incipient-nucleation behavior and role of system size. Phys. Rev. E 92, 032132 (2015).

  28. 28.

    Limmer, D. T. & Chandler, D. Corresponding states for mesostructure and dynamics of super cooled water. Faraday Discuss. 167, 485–498 (2013).

  29. 29.

    Sidhu, S. S., Heaton, L. R., Zauberis, D. D. & Campos, F. P. Neutron diffraction study of titanium–zirconium system. J. Appl. Phys. 27, 1040–1042 (1956).

  30. 30.

    Khvostantsev, L. G. A verkh–niz (up–down) toroid device for generation of high pressure. High Temp. High Press. 16, 165–169 (1984).

  31. 31.

    Ripmeester, J. A. & Alavi, S. Some current challenges in clathrate hydrate science: nucleation, decomposition and the memory effect. Curr. Opin. Solid State Mater. Sci. 20, 344–351 (2016).

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This research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. We thank the Sloan Foundation’s Deep Carbon Observatory for supporting this work.

Author information

C.A.T. conceived and designed the experiment. C.A.T., J.J.M. and A.R.M. conducted the experiment. C.A.T. and D.D.K. analysed the data. C.A.T., D.D.K and C.E.M. wrote the manuscript.

Competing interests

The authors declare no competing interests.

Correspondence to Chris A. Tulk.

Extended data figures and tables

  1. Extended Data Fig. 1 Pressure–load curve of a sample mixed with lead.

    It should be noted that this curve is not from the dataset presented in Fig. 2, as that sample contained no lead. Thus, no direct one-to-one comparison can be made.

  2. Extended Data Fig. 2 Data from separate experimental run, showing the crystallographic transformation sequence.

    Initial compression of ice Ih, showing the crystalline sequence of transitions at 100 K. In the initial runs, the cooled sample was predominantly composed of ice Ih with a small amount of ice IX; hence the ‘sealing’ load that was applied to the gasket was slightly too high, and upon cooling the pressure was such that high-pressure crystalline phases were present. To remove ice IX, the sample was melted at 275 K and the pressure was reduced to atmospheric. Upon re-cooling the sample was determined to be pure ice Ih, as shown in the figure. The data shown in Fig. 2b were obtained from a subsequent loading, with a fresh sample in an unused gasket cooled to 100 K under a small sealing load; no ice IX was found to be present until initial compression at 100 K.

  3. Extended Data Fig. 3 d-spacing plot of amorphization/recrystallization transformation.

    Transformation of pure ice Ih to HDA and recrystallization to ice VII′ with some remnant HDA. In this case the sample was pressurized directly to 15 kbar in 1,740 s at 100 K. These datasets have been normalized to vanadium.

  4. Extended Data Fig. 4 Higher-resolution plot of crystal phases.

    Comparison of initial ice Ih with ice XV and ice VIII′. The sample was pressurized slowly with 1-h isobaric breaks to collect diffraction data. The data were collected using a detector at a greater diffraction angle, thus providing increased resolution at the expense of the momentum-transfer range. These datasets have been normalized to vanadium.

  5. Extended Data Fig. 5 Resulting high-pressure crystal phases.

    Comparison of the crystal phases resulting from the transformation of ice XV to ice VIII′ and from re-crystallization of HDA ice. All datasets were collected at 100 K.

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Fig. 1: Phase diagrams of crystalline ice and liquid and amorphous water.
Fig. 2: Diffraction data of amorphous and crystalline ice for increasing pressure at 100 K.
Fig. 3: Amorphous and crystalline structural progression of ice when compressed at 100 K.
Extended Data Fig. 1: Pressure–load curve of a sample mixed with lead.
Extended Data Fig. 2: Data from separate experimental run, showing the crystallographic transformation sequence.
Extended Data Fig. 3: d-spacing plot of amorphization/recrystallization transformation.
Extended Data Fig. 4: Higher-resolution plot of crystal phases.
Extended Data Fig. 5: Resulting high-pressure crystal phases.


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