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Doping-induced disappearance of ice II from water’s phase diagram

Nature Physicsvolume 14pages569572 (2018) | Download Citation


Water and the many phases of ice display a plethora of complex physical properties and phase relationships1,2,3,4 that are of paramount importance in a range of settings including processes in Earth’s hydrosphere, the geology of icy moons, industry and even the evolution of life. Well-known examples include the unusual behaviour of supercooled water2, the emergent ferroelectric ordering in ice films4 and the fact that the ‘ordinary’ ice Ih floats on water. We report the intriguing observation that ice II, one of the high-pressure phases of ice, disappears in a selective fashion from water’s phase diagram following the addition of small amounts of ammonium fluoride. This finding exposes the strict topologically constrained nature of the ice II hydrogen-bond network, which is not found for the competing phases. In analogy to the behaviour of frustrated magnets5, the presence of the exceptional ice II is argued to have a wider impact on water’s phase diagram, potentially explaining its general tendency to display anomalous behaviour. Furthermore, the impurity-induced disappearance of ice II raises the prospect that specific dopants may not only be able to suppress certain phases but also induce the formation of new phases of ice in future studies.

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Change history

  • 11 April 2018

    In the version of this Letter originally published, the citation to ref. 30 in the Fig. 1 caption should have been to ref. 29, and the citation to ref. 29 in the Methods should have been to ref. 30.


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We thank the Royal Society (UF150665) and the Leverhulme Trust (RPG-2014-04) for funding, the ISIS facility for granting access to the PEARL instrument, C. Ridley for help with the PEARL pressure equipment, M. Vickers for help with the X-ray measurements, J. K. Cockcroft for access to the Cryojet, and S. L. Price, A. K. Soper and P. A. McClarty for helpful discussions. We also acknowledge the use of the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk) through the Materials Chemistry Consortium via EPSRC grant no. EP/L000202 and the EPSRC-funded Centre for Doctoral Training in Advanced Characterisation of Materials for a studentship (EP/L015277/1).

Author information


  1. Department of Chemistry, University College London, London, UK

    • Jacob J. Shephard
    • , Ben Slater
    • , Peter Harvey
    • , Martin Hart
    •  & Christoph G. Salzmann
  2. ISIS Facility, Rutherford Appleton Laboratory, Didcot, UK

    • Craig L. Bull
  3. London Centre for Nanotechnology and Department of Physics & Astronomy, University College London, London, UK

    • Steven T. Bramwell


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C.G.S. designed the project; J.J.S. and P.H. conducted the laboratory-based experiments and performed data analyses; C.G.S., J.J.S, M.H. and C.L.B. carried out the neutron diffraction experiments; C.G.S. analysed the neutron diffraction data; S.T.B. and C.G.S developed the statistical mechanics aspects of this work; DFT calculations were carried out by B.S.; C.G.S, S.T.B., B.S. and J.J.S. wrote the manuscript and prepared the figures; all authors discussed the results and commented on the manuscript.

Competing interests

The authors declare no competing interests.

Corresponding author

Correspondence to Christoph G. Salzmann.

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