Abstract
Although several studies1,2 of ordinary ice (Ih) have established its nearly perfect oxygen arrangement and the statistical distribution of hydrogen among two symmetrically equivalent sites (the ‘half-hydrogen’ model3), several fundamental problems remain. The O—H bond length found in ice Ih is considerably larger than in other polymorphs of ice determined precisely4,5, and many arguments have been put forward against the value observed5,6. Similarly, the tetrahedral H—O—H bond angle in ice Ih differs considerably from the value observed in the vapour phase, and this led Chidambaram7 to propose a bent hydrogen bond model which further splits the atom positions, and which has not yet been verified. Finally, the mean shape of the double potential governing the atom distribution and the barrier governing the mobility still remain to be evaluated. We show here how high-precision, short-wavelength neutron diffraction data from ice Ih can be used to evaluate the molecular structure and atomic density distribution at 60 K. The unusually long O—H distance is confirmed, but there is no evidence for bent hydrogen bonds. Indeed the hydrogen atom density distribution is well described by a librational motion of the hydrogen atom around the oxygen. The mean barrier height between the ‘half-hydrogen’ atom positions was obtained from the scattering density as 0.012 eV, which implies that the zero point motion is of high importance for the proton exchange at low temperatures.
Similar content being viewed by others
References
Peterson, S. W. & Levy, H. A. Acta crystallogr. 10, 70–76 (1957).
Chamberlain, J. S., Moore, F. H. & Fletcher, N. H. in Physics and Chemistry of Ice (eds Whalley, E. et al.) (Royal Society of Canada, Ottawa, 1973).
Pauling, L. J. Am. chem. Soc. 57, 2680–2684 (1935).
Kamb, B., Hamilton, W. C., La Placa, S. J. & Prakash, A. J. chem. Phys. 55, 1934–1945 (1971).
La Placa, S. J., Hamilton, W. C., Kamb, B. & Prakash, A. J. chem. Phys. 58, 567–580 (1973).
Whalley, E. Molec. Phys. 28, 1105–1108 (1974).
Chidambaram, R. Acta crystallogr. 14, 467–468 (1961).
Lehmann, M. S. & Larsen, F. K. Acta crystallogr. A 30, 580–584 (1974).
Coppens, P. in Crystallographic Computing (Munskgaard, Copenhagen, 1970).
Merisalo, M. & Kuritta, J. J. appl. Crystallogr. 11, 179–183 (1978).
Becker, J. P. & Coppens, P. Acta crystallogr. A 31, 417–425 (1975).
Brill, R. & Tippe, A. Acta crystallogr. 23, 343–345 (1967).
Zucker, U. H., Perenthaler, E., Kuhs, W. F. & Schulz, H. The Prometheus-System (available from the authors, 1981).
Johnson, C. K. & Levy, H. A. in International Tables for X-ray Crystallography Vol. 4 (eds Ibers, J. A. & Hamilton, W.C.) (Kynoch, Birmingham, 1974).
Hamilton, W. C. Acta crystallogr. 18, 502–510 (1965).
Bertie, J. E. & Whalley, E. J. chem. Phys. 40, 1637–1645 (1964).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Kuhs, W., Lehmann, M. Bond-lengths, bond angles and transition barrier in ice Ih by neutron scattering. Nature 294, 432–434 (1981). https://doi.org/10.1038/294432a0
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1038/294432a0
- Springer Nature Limited
This article is cited by
-
Molecular insight into the initial hydration of tricalcium aluminate
Nature Communications (2024)
-
Friction and a Tribochemical Reaction between Ice and Hexagonal Boron Nitride: A Theoretical Study
Tribology Letters (2008)
-
Direct determination of the intramolecular O–D distance in ice Ih and Ic by neutron diffraction
Nature (1987)
-
Flip-flop hydrogen bonding in a partially disordered system
Nature (1982)