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Molecular dynamics simulation of the ice nucleation and growth process leading to water freezing

Nature volume 416, pages 409–413 (2002)Cite this article

Abstract

Upon cooling, water freezes to ice. This familiar phase transition occurs widely in nature, yet unlike the freezing of simple liquids1,2,3, it has never been successfully simulated on a computer. The difficulty lies with the fact that hydrogen bonding between individual water molecules yields a disordered three-dimensional hydrogen-bond network whose rugged and complex global potential energy surface4,5,6 permits a large number of possible network configurations. As a result, it is very challenging to reproduce the freezing of ‘real’ water into a solid with a unique crystalline structure. For systems with a limited number of possible disordered hydrogen-bond network structures, such as confined water, it is relatively easy to locate a pathway from a liquid state to a crystalline structure7,8,9. For pure and spatially unconfined water, however, molecular dynamics simulations of freezing are severely hampered by the large number of possible network configurations that exist. Here we present a molecular dynamics trajectory that captures the molecular processes involved in the freezing of pure water. We find that ice nucleation occurs once a sufficient number of relatively long-lived hydrogen bonds develop spontaneously at the same location to form a fairly compact initial nucleus. The initial nucleus then slowly changes shape and size until it reaches a stage that allows rapid expansion, resulting in crystallization of the entire system.

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Figure 1: The total potential energies of the instantaneous structures in the trajectory for 512 water molecules after quenching (at t = 0 ns) from higher temperature to 230 K.
Figure 2: The hydrogen bond network structure of water at a given time in inherent structures.
Figure 3: Number of water molecules having long-lasting hydrogen bonds (τlife > 2 ns) and the size of the largest cluster in inherent structures.
Figure 4: Asphericity and size of the largest cluster.

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Acknowledgements

We thank J. Jortner, and S. Sastry for many stimulating discussions and encouragement. We also thank H. Tanaka, A. Baba and H. Inagaki for cooperative work and valuable discussions. The present study is partially supported by the Grant-in-Aid Scientific Research on Priority Area of ‘Condensed Phase Chemical Reaction Dynamics’, and by the Grant-in-Aid for Scientific Research. Calculations were carried out at the Nagoya University Computation Center and the Research Center for Computational Science.

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  1. Chemistry Department, Nagoya University, Chikusa-ku, 464-8602, Nagoya, Japan

    Masakazu Matsumoto, Shinji Saito & Iwao Ohmine

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  1. Masakazu Matsumoto
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Correspondence to Iwao Ohmine.

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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). https://doi.org/10.1038/416409a

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