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Crystalline ice

Amorphous on the surface

Nature Materials volume 10, pages 725–726 (2011)Cite this article

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Crystalline ice surfaces are found to exhibit an unusually large spread of vacancy formation energies, akin to an amorphous material. The finding has implications for the fundamental understanding of electrostatically frustrated surfaces and for the reactivity and catalytic properties of atmospheric ice.

The reason behind the surprisingly large variation in vacancy formation energies for the surface layers lies in the fact that a molecule of water, far from being a sphere that bonds uniformly to its neighbours, participates in up to four highly directional hydrogen bonds arranged in an approximately tetrahedral geometry around the oxygen atom. Because each particular bond can be only either donated or accepted, a multitude of different hydrogen-bond arrangements is possible, each with a different total bonding energy. In the bulk of ordinary hexagonal ice, the variation in energy resulting from different bond arrangements is small, on the order of a few tenths of a kJ per mol (this is related to the enthalpy of the transition from a hydrogen-bond disordered phase with well-defined residual configurational entropy to a lower-temperature, proton-ordered phase with near zero configurational entropy2). However, when interfaces are present, such as in water clusters3 or ice surfaces4, differences in energy of an order of magnitude larger than in the bulk can occur.

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Figure 1: Molecular representation of the crystalline surface of hexagonal ice, with a water molecule hovering above a vacancy defect.
Figure 2: Variation in vacancy formation energies of water molecules in the six bilayers closest to the surface of hexagonal ice1.

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  1. Lars Ojamäe is in the Department of Chemistry, IFM, Linköping University, SE-581 82 Linköping, Sweden.,

    Lars Ojamäe

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  1. Lars Ojamäe
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Correspondence to Lars Ojamäe.

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Ojamäe, L. Amorphous on the surface. Nature Mater 10, 725–726 (2011). https://doi.org/10.1038/nmat3129

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