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Structural transformation in supercooled water controls the crystallization rate of ice

Abstract

One of water’s unsolved puzzles is the question of what determines the lowest temperature to which it can be cooled before freezing to ice. The supercooled liquid has been probed experimentally to near the homogeneous nucleation temperature, TH ≈ 232 K, yet the mechanism of ice crystallization—including the size and structure of critical nuclei—has not yet been resolved. The heat capacity and compressibility of liquid water anomalously increase on moving into the supercooled region, according to power laws that would diverge (that is, approach infinity) at 225 K (refs 1, 2), so there may be a link between water’s thermodynamic anomalies and the crystallization rate of ice. But probing this link is challenging because fast crystallization prevents experimental studies of the liquid below TH. And although atomistic studies have captured water crystallization3, high computational costs have so far prevented an assessment of the rates and mechanism involved. Here we report coarse-grained molecular simulations with the mW water model4 in the supercooled regime around TH which reveal that a sharp increase in the fraction of four-coordinated molecules in supercooled liquid water explains its anomalous thermodynamics and also controls the rate and mechanisms of ice formation. The results of the simulations and classical nucleation theory using experimental data suggest that the crystallization rate of water reaches a maximum around 225 K, below which ice nuclei form faster than liquid water can equilibrate. This implies a lower limit of metastability of liquid water just below TH and well above its glass transition temperature, 136 K. By establishing a relationship between the structural transformation in liquid water and its anomalous thermodynamics and crystallization rate, our findings also provide mechanistic insight into the observed5 dependence of homogeneous ice nucleation rates on the thermodynamics of water.

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Figure 1: Evolution of the thermodynamics and structure of water on cooling.
Figure 2: Kinetics of ice crystallization and critical ice nuclei.

References

  1. 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 

  2. Tombari, E., Ferrari, C. & Salvetti, G. Heat capacity anomaly in a large sample of supercooled water. Chem. Phys. Lett. 300, 749–751 (1999)

    Article  ADS  CAS  Google Scholar 

  3. Matsumoto, M., Saito, S. & Ohmine, I. Molecular dynamics simulation of the ice nucleation and growth process leading to water freezing. Nature 416, 409–413 (2002)

    Article  ADS  CAS  Google Scholar 

  4. Molinero, V. & Moore, E. B. Water modeled as an intermediate element between carbon and silicon. J. Phys. Chem. B 113, 4008–4016 (2009)

    Article  CAS  Google Scholar 

  5. Koop, T., Luo, B. P., Tsias, A. & Peter, T. Water activity as the determinant for homogeneous ice nucleation in aqueous solutions. Nature 406, 611–614 (2000)

    Article  ADS  CAS  Google Scholar 

  6. Finney, J. L., Hallbrucker, A., Kohl, I., Soper, A. K. & Bowron, D. T. Structures of high and low density amorphous ice by neutron diffraction. Phys. Rev. Lett. 88, 225503 (2002)

    Article  ADS  CAS  Google Scholar 

  7. Moore, E. B. & Molinero, V. Growing correlation length in supercooled water. J. Chem. Phys. 130, 244505 (2009)

    Article  ADS  Google Scholar 

  8. Mallamace, F. et al. The anomalous behavior of the density of water in the range 30K < T 373K. Proc. Natl Acad. Sci. USA 104, 18387–18391 (2007)

    Article  ADS  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  10. Huang, C. et al. Increasing correlation length in bulk supercooled HO, DO, and NaCl solution determined from small angle x-ray scattering. J. Chem. Phys. 133, 134504 (2010)

    Article  ADS  Google Scholar 

  11. Kohl, I., Mayer, E. & Hallbrucker, A. The glass water-cubic ice system: a comparative study by X-ray diffraction and differential scanning calorimetry. Phys. Chem. Chem. Phys. 2, 1579–1586 (2000)

    Article  CAS  Google Scholar 

  12. Stevenson, J. D. & Wolynes, P. G. The ultimate fate of supercooled liquids. J. Phys. Chem. A 115, 3713–3719 (2011)

    Article  CAS  Google Scholar 

  13. Moore, E. B., de la Llave, E., Welke, K., Scherlis, D. A. & Molinero, V. Freezing, melting and structure of ice in a hydrophilic nanopore. Phys. Chem. Chem. Phys. 12, 4124–4134 (2010)

    Article  CAS  Google Scholar 

  14. Jähnert, S. et al. Melting and freezing of water in cylindrical silica nanopores. Phys. Chem. Chem. Phys. 10, 6039–6051 (2008)

    Article  Google Scholar 

  15. Wedekind, J., Strey, R. & Reguera, D. New method to analyze simulations of activated processes. J. Chem. Phys. 126, 134103 (2007)

    Article  ADS  Google Scholar 

  16. Liu, J., Nicholson, C. E. & Cooper, S. J. Direct measurement of critical nucleus size in confined volumes. Langmuir 23, 7286–7292 (2007)

    Article  CAS  Google Scholar 

  17. Tanaka, H. Possible resolution of the Kauzmann paradox in supercooled liquids. Phys. Rev. E 68, 011505 (2003)

    Article  ADS  Google Scholar 

  18. Xu, L. et al. Appearance of a fractional Stokes-Einstein relation in water and a structural interpretation of its onset. Nature Phys. 5, 565–569 (2009)

    Article  ADS  CAS  Google Scholar 

  19. Kauzmann, W. The nature of the glassy state and the behavior of liquids at low temperatures. Chem. Rev. 43, 219–256 (1948)

    Article  CAS  Google Scholar 

  20. Kiselev, S. Physical limit of stability in supercooled liquids. Int. J. Thermophys. 22, 1421–1433 (2001)

    Article  CAS  Google Scholar 

  21. Angell, C. A. Insights into phases of liquid water from study of its unusual glass-forming properties. Science 319, 582–587 (2008)

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  23. 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 

  24. Sastry, S., Debenedetti, P. G. & Sciortino, F. Singularity-free interpretation of the thermodynamics of supercooled water. Phys. Rev. B 53, 6144–6154 (1996)

    Article  ADS  CAS  Google Scholar 

  25. Mishima, O. & Stanley, H. E. The relationship between liquid, supercooled and glassy water. Nature 396, 329–335 (1998)

    Article  ADS  CAS  Google Scholar 

  26. Mishima, O. Application of polyamorphism in water to spontaneous crystallization of emulsified LiCl–H2O solution. J. Chem. Phys. 123, 154506 (2005)

    Article  ADS  Google Scholar 

  27. Moore, E. B. & Molinero, V. Ice crystallization in water's “no-man's land”. J. Chem. Phys. 132, 244504 (2010)

    Article  ADS  Google Scholar 

  28. Liu, Y., Panagiotopoulos, A. Z. & Debenedetti, P. G. Low-temperature fluid-phase behavior of ST2 water. J. Chem. Phys. 131, 104508 (2009)

    Article  ADS  Google Scholar 

  29. Limmer, D. T. & Chandler, D. The putative liquid-liquid transition is a liquid-solid transition in atomistic models of water. J. Chem. Phys. 135, 134503 (2011)

    Article  ADS  Google Scholar 

  30. Plimpton, S. J. Fast parallel algorithms for short-range molecular dynamics. J. Comput. Phys. 117, 1–19 (1995)

    Article  ADS  CAS  Google Scholar 

  31. de La Llave, E., Molinero, V. & Scherlis, D. A. Water filling of hydrophilic nanopores. J. Chem. Phys. 133, 034513 (2010)

    Article  ADS  Google Scholar 

  32. Jacobson, L. C., Hujo, W. & Molinero, V. Thermodynamic stability and growth of guest-free clathrate hydrates: a low-density crystal phase of water. J. Phys. Chem. B 113, 10298–10307 (2009)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the Arnold and Mabel Beckman Foundation through a Young Investigator Award to V.M. We thank P. G. Debenedetti for discussions and D. P. Fernandez for criticism of the manuscript.

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Contributions

V.M. conceived and designed the study and wrote the paper. E.B.M. and V.M. performed the simulations, analysed the data and interpreted the results.

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Correspondence to Valeria Molinero.

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The authors declare no competing financial interests.

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Moore, E., Molinero, V. Structural transformation in supercooled water controls the crystallization rate of ice. Nature 479, 506–508 (2011). https://doi.org/10.1038/nature10586

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