Abstract
Because of its open hydrogen-bonded structure, ice shows many structural changes between different crystalline forms under high pressure. Crystallographic studies of these transitions have been pursued largely by neutron scattering, which allows the positions of the hydrogen atoms to be identified1,2. Such studies have previously been extended to pressures of up to 20?GPa, which is however insufficient to permit the investigation of ice X, a ‘symmetric ice’ in which the protons are thought to reside midway between the oxygen atoms3,4,5. So far, information about ice X has therefore come from indirect methods such as infrared6,7 or Brillouin8 spectroscopy. Here we show that single-crystal X-ray diffraction is able to reveal the signature of hydrogen-bond symmetrization. The 111 reflection can be assigned to the hydrogen atoms alone, and we can measure it up to 170?GPa in a diamond anvil cell. This diffraction line (normalized against the intensity of the 222 line, which is due mostly to oxygen atoms) indicates that the proton centring in ice X occurs from about 60 to 150?GPa; at this latter pressure the intensity increases sharply, signalling a further structural change. At lower pressures, we see ice VII ordering in a sequence of spatially modulated phases between 2.2 and 25?GPa, which suggests an analogy with the incommensurate phases of the frustrated Ising model9.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 51 print issues and online access
$199.00 per year
only $3.90 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
1. Kuhs, W. F., Finney, J. L., Vettier, C. & Bliss, D. V. Structure and hydrogen ordering in ices VI, VII and VIII by neutron powder diffraction. J. Chem. Phys. 81, 3612–3623 (1984).
2. Nelmes, R. J., Loveday, J. S., Marshall, W. G., Hamel, G., Besson, J. N. & Klotz, S. Multisite disordered structure of ice VII to 20?GPa. Phys. Rev. Lett. 81, 2719–2722 (1998).
3. Holzapfel, W. B. On the symmetry of the hydrogen bonds in ice VII. J. Chem. Phys. 56, 712–715 (1972).
4. Schweizer, K. S. & Stillinger, F. H. High pressure phase transitions and hydrogen-bond symmetry in ice polymorphs. J. Chem. Phys. 80, 1230–1240 (1984).
5. Benoit, M., Marx, D. & Parrinello, M. Tunnelling and zero-point motion in high-pressure ice. Nature 392, 258–261 (1998).
6. Aoki, K., Yamawaki, H., Sakashita, M. & Fujihisa, H. Infrared absorption study of the hydrogen-bond symmetrization in ice to 100?GPa. Phys. Rev. B 54, 15673–15677 (1996).
7. Goncharov, A. F., Struzhkin, V. V., Somayazulu, M. S., Hemley, R. J. & Mao, H. K. Compression of ice to 210 Gigapascals: Infrared evidence for a symmetric hydrogen-bonded phase. Science 273, 218–220 (1996).
8. Polian, A. & Grimsditch, M. New high pressure phase of H2O: Ice X. Phys. Rev. Lett. 52, 1312–1314 (1984).
9. Bak, P. & von Boehm, J. Ising model with solitons, phasons and ‘the devil's staircase’. Phys. Rev. B 21, 5297–5308 (1980).
10. Loubeyre, P.et al. X-ray diffraction and equation of state of hydrogen at megabar pressures. Nature 383, 702–704 (1996).
11. Hemley, R. J.et al. Static compression of H2O-ice to 128?GPa. Nature 330, 737–740 (1987).
12. Wolanin, E.et al. Equation of state of ice VII up to 106?GPa. Phys. Rev. B 56, 5781–5785 (1997).
13. Aubry, S. Devil's staircase and order without periodicity in classical condensed matter. J. Phys. (Paris) 44, 147–162 (1983).
14. Nelmes, R. J.et al. Neutron diffraction study of the structure of deuterated ice VIII to 10?GPa. Phys. Rev. Lett. 71, 1192–1195 (1993).
15. Bernasconi, M., Silvestrelli, P. L. & Parrinello, M. Ab-initio infrared absorption study of the hydrogen-bond symmetrization in ice. Phys. Rev. Lett. 81, 1235–1238 (1998).
16. Benoit, M., Bernasconi, M., Focher, P. & Parinello, M. New high pressure phase of ice. Phys. Rev. Lett. 76, 2934–2936 (1996).
17. Vinet, P., Ferrante, J., Smith, J. R. & Rose, J. H. Auniversal equation of state for solids. J. Phys. C 19, L467–L473 (1986).
18. Mao, H. K., Bell, P. M., Shaner, J. & Steinberg, D. Specific volume meausrements of Cu, Mo, Pd and Ag and calibration of the ruby R1 fluorescence pressure gauge from 0.06 to 1?Mbar. J. Appl. Phys. 49, 3276–3283 (1978).
19. Datchi, F., LeToullec, R. & Loubeyre, P. Improved calibration of the SrB4O7:Sm2+ optical pressure gauge: Advantages at very high pressures and high temperatures. J. Appl. Phys. 81, 3333–3339 (1997).
20. Anderson, O. L., Isaak, O. & Yamamoto, S. Anharmonicity and the equation of state of gold. J. Appl. Phys. 65, 1534–1543 (1989).
21. Shimizu, H., Nabetani, T., Nishiba, T. & Sasaki, S. High pressure elastic properties of the VI and VII phase of ice in dense H2O and D2O. Phys. Rev. B 53, 6107–6110 (1996).
Acknowledgements
We thank J. Loveday for the computation of the effect of oxygen disorder and proton tunnelling on the structure factor, F. Datchi for help in the experiments and the ESRF staff for technical support. We also thank Y. Petroff for continuous interest in this work, and Ph. Pruzan and J. M. Besson for discussions. We acknowledge a referee for suggesting the interpretation of the rise in I111/I222at 150?GPA.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Loubeyre, P., LeToullec, R., Wolanin, E. et al. Modulated phases and proton centring in ice observed by X-ray diffraction up to 170?GPa. Nature 397, 503–506 (1999). https://doi.org/10.1038/17300
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1038/17300
This article is cited by
-
Thermodynamics of high-pressure ice phases explored with atomistic simulations
Nature Communications (2022)
-
Dynamic compression of water to conditions in ice giant interiors
Scientific Reports (2022)
-
Nanosecond X-ray diffraction of shock-compressed superionic water ice
Nature (2019)
-
Experimental evidence for superionic water ice using shock compression
Nature Physics (2018)
-
Observation of nuclear quantum effects and hydrogen bond symmetrisation in high pressure ice
Nature Communications (2018)
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.
