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Surface premelting of water ice

Abstract

Frozen water has a quasi-liquid layer at its surface that exists even well below the bulk melting temperature; the formation of this layer is termed premelting. The nature of the premelted surface layer, its structure, thickness and how the layer changes with temperature have been debated for over 160 years, since Faraday first postulated the idea of a quasi-liquid layer on ice. Here, we briefly review current opinions and evidence on premelting at ice surfaces, gathering data from experiments and computer simulations. In particular, spectroscopy, microscopy and simulation have recently made important contributions to our understanding of this field. The identification of premelting inhomogeneities, in which portions of the surface are quasi-liquid-like and other parts of the surface are decorated with liquid droplets, is an intriguing recent development. Untangling the interplay of surface structure, supersaturation and surface defects is currently a major challenge. Similarly, understanding the coupling of surface structure with reactivity at the surface and crystal growth is a pressing problem in understanding the behaviour and formation of ice on Earth.

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Fig. 1: Crystal and surface structures of ice.
Fig. 2: The varied morphologies of hexagonal ice (Ih).
Fig. 3: A selective overview of estimates of approximate QLL thickness obtained from physical measurement.
Fig. 4: Timeline of some of the key developments in unravelling the nature of the QLL of ice, as selected by the authors.
Fig. 5: Inhomogeneity in the outer two bilayers of ice.
Fig. 6: The emergence of two distinct and immiscible QLLs over an ice surface.
Fig. 7: Heterogeneity in the QLL obtained through grand canonical molecular dynamics.

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Acknowledgements

The authors thank J. Abbatt, T. Bartels-Rausch and E. Wolff for helpful information in compiling this Review. B.S. and A.M. thank C. Vega, M. Fitzner, C. Salzmann, E. Wang and, in particular, L. Macdowell for helpful comments on this Review. The constructive reviews from referees are also acknowledged. The work of A.M. is supported by the European Research Council (ERC) under the European Union’s Seventh Framework Programme: Grant Agreement number 616121 (HeteroIce).

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Nature Reviews Chemistry thanks V. Molinero and the other anonymous reviewer(s) for their contribution to the peer review of this work.

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Slater, B., Michaelides, A. Surface premelting of water ice. Nat Rev Chem 3, 172–188 (2019). https://doi.org/10.1038/s41570-019-0080-8

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