Tunnelling and zero-point motion in high-pressure ice

Magali Benoit, Dominik Marx () and Michele Parrinello
Additional contact information
Magali Benoit: Laboratoire des Verres, Université
Dominik Marx: Max-Planck-Institut für Festkörperforschung
Michele Parrinello: Max-Planck-Institut für Festkörperforschung

Nature, 1998, vol. 392, issue 6673, 258-261

Abstract: 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.

Date: 1998
References: Add references at CitEc
Citations: View citations in EconPapers (2)

Downloads: (external link)
https://www.nature.com/articles/32609 Abstract (text/html)
Access to the full text of the articles in this series is restricted.

Related works:
This item may be available elsewhere in EconPapers: Search for items with the same title.

Export reference: BibTeX RIS (EndNote, ProCite, RefMan) HTML/Text

Persistent link: https://EconPapers.repec.org/RePEc:nat:nature:v:392:y:1998:i:6673:d:10.1038_32609

Ordering information: This journal article can be ordered from
https://www.nature.com/

DOI: 10.1038/32609

Access Statistics for this article

Nature is currently edited by Magdalena Skipper

More articles in Nature from Nature
Bibliographic data for series maintained by Sonal Shukla () and Springer Nature Abstracting and Indexing ().