Abstract
The microscopic structure of ice poses a long-standing challenge to theory1,2,3. Because of their low mass, the protons in the hydrogen bonds that define the structures of crystalline ice are susceptible to quantum-mechanical effects such as tunnelling1,4,5,6,7,8. High pressure provides a means of controlling the length of the hydrogen bonds in order to investigate such effects. In particular, Holzapfel predicted 26 years ago that, under pressure, hydrogen bonds might be transformed from the highly asymmetric O–H···O configuration to a symmetric state in which the proton lies midway between the two oxygens9, leading to a non-molecular symmetric phase of ice, now denoted as ice ‘X’. The existence of this phase has been inferred from spectroscopy10,11,12,13,14, but has still not been observed directly. Here we investigate the role of quantum effects in proton ordering and hydrogen-bond symmetrization within ice at high pressure by using a simulation technique that treats both electrons and nuclei quantum-mechanically15,16,17. We find that the proton-ordered structure at low pressure, with asymmetric hydrogen bonds (ice VIII), transforms on increasing pressure to a proton-disordered asymmetric phase (ice VII) owing to translational proton tunnelling. On further compression, the zero-point fluctuations lead to strongly delocalized protons and hydrogen-bond symmetrization, even though the underlying character of the proton-transfer potential remains a double well. Only at still higher pressures does the double-well potential become transformed into a single well, whereupon the protons again become increasingly localized.
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Acknowledgements
Our warm thanks to M. Tuckerman, J. Hutter, U. Schwarz, M. Bernasconi and S.Klotz for useful discussions. The simulations were carried out on the IBM SP2 at CNUSC (Montpellier) and at MPI Stuttgart.
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Benoit, M., Marx, D. & Parrinello, M. Tunnelling and zero-point motion in high-pressure ice. Nature 392, 258–261 (1998). https://doi.org/10.1038/32609
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DOI: https://doi.org/10.1038/32609
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