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New metastable form of ice and its role in the homogeneous crystallization of water

Nature Materials volume 13, pages 733–739 (2014)Cite this article

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Abstract

The homogeneous crystallization of water at low temperature is believed to occur through the direct nucleation of cubic (Ic) and hexagonal (Ih) ices. Here, we provide evidence from molecular simulations that the nucleation of ice proceeds through the formation of a new metastable phase, which we name Ice 0. We find that Ice 0 is structurally similar to the supercooled liquid, and that on growth it gradually converts into a stacking of Ice Ic and Ih. We suggest that this mechanism provides a thermodynamic explanation for the location and pressure dependence of the homogeneous nucleation temperature, and that Ice 0 controls the homogeneous nucleation of low-pressure ices, acting as a precursor to crystallization in accordance with Ostwald’s step rule of phases. Our findings show that metastable crystalline phases of water may play roles that have been largely overlooked.

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Figure 1: A new metastable ice phase and its role in the mW phase diagram.
Figure 2: Microscopic pathway of ice crystallization.
Figure 3: Snapshots from a crystallization trajectory at T = 206 K and ambient pressure.

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Acknowledgements

We are grateful to F. Sciortino for a critical reading of the manuscript and to J. Doye and A. Reinhardt for useful discussions. This study was partly supported by Grants-in-Aid for Scientific Research (S) and Specially Promoted Research from the Japan Society for the Promotion of Science (JSPS), the Aihara Project, the FIRST programme from JSPS, initiated by the Council for Science and Technology Policy (CSTP), a JSPS short-term fellowship for F.R., and a JSPS Postdoctoral Fellowship for J.R.

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Author notes

  1. John Russo and Flavio Romano: These authors contributed equally to this work.

Authors and Affiliations

  1. Institute of Industrial Science, University of Tokyo, 4-6-1 Komaba, Meguro-ku Tokyo 153-8505, Japan,

    John Russo, Flavio Romano & Hajime Tanaka

  2. Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road Oxford OX1 3QZ, UK,

    Flavio Romano

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  1. John Russo
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Contributions

J.R. and F.R. performed the numerical simulations and the data analysis. H.T. proposed and supervised the study. All authors discussed the results and contributed to the writing of the manuscript.

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Correspondence to Hajime Tanaka.

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The authors declare no competing financial interests.

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Russo, J., Romano, F. & Tanaka, H. New metastable form of ice and its role in the homogeneous crystallization of water. Nature Mater 13, 733–739 (2014). https://doi.org/10.1038/nmat3977

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