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Immobility of protons in ice from 30 to 190 K

Nature volume 398, pages 405–407 (1999)Cite this article

Abstract

The anomalously fast motion of hydronium ions (H3O+) in water is often attributed to the Grotthuss mechanism1,2, whereby protons tunnel from one water molecule to the next. This tunnelling is relevant to proton motion through water in restricted geometries, such as in ‘proton wires’ in proteins3 and in stratospheric ice particles4. Transport of hydronium ions in ice is thought to be closely related to its transport in water1,2. But whereas claims have been made that such tunnelling can persist even at 0 K in ice5,6,7, counter-claims suggest that the activation energy for hydronium motion in ice is non-zero8,9,10. Here we use ‘soft-landing’11,12,13 of hydronium ions on the surface of ice to show that the ions do not seem to move at all at temperatures below 190 K. This implies not only that hydronium motion is an activated process, but also that it does not occur at anything like the rate expected from the Grotthuss mechanism. We also observe the motion of an important kind of defect in ice's hydrogen-bonded structure (the D defect). Extrapolation of our measurements to 0 K indicates that the defect is still mobile at this temperature, in an electric field of 1.6 × 108 V m−1.

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Figure 1: Ice structure and transport.
Figure 2: Lack of diffusion of hydronium ions in water ice.
Figure 3: Evidence for hydrogen-bond defect motion.
Figure 4: Hydrogen-bond defect motion versus electric field.

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References

  1. Hobbs, P. V. Ice Physics (Clarendon, Oxford, (1974).

    Google Scholar 

  2. Whalley, E., Jones, S. J. & Gold, L. W. (eds) Physics and Chemistry of Ice (Royal Soc. Canada, Ottawa, (1973).

    Google Scholar 

  3. Pomes, R. & Roux, B. Structure and dynamics of a proton wire: A theoretical study of H+ translocation along the single-file water chain in the gramicidin A channel. Biophys. J. 71, 19–39 (1996).

    Article  ADS  CAS  Google Scholar 

  4. Bainco, R., Gertner, B. J. & Hynes, J. T. Proton transfer reactions at the surface of ice. Heterogeneous reactions involved in stratospheric ozone deletion. Ber. Bunsenges. Phys. Chem. 102, 518–526 (1998).

    Article  Google Scholar 

  5. Eckener, U., Helmreich, D. & Engelhardt, H. in Physics and Chemistry of Ice (eds Whalley, E., Jones S. J. & Gold, L. W.) 242–245 (Royal Soc. Canada, Ottawa, (1973).

    Google Scholar 

  6. Petrenko, V. F. & Maeno, N. Ice field transistor. J. de Phys. C 48, 115–119 ( 1987).

    Google Scholar 

  7. Petrenko, V. F. Electrical Properties of Ice (Spec. Rep. 93-20, US Army Cold Regions Research and Engineering Laboratory, Hanover, NH, (1993).

    Google Scholar 

  8. Collier, W. B., Ritzhaupt, G. & Devlin, J. P. Spectroscopically evaluated rates and energies for proton transfer and Bjerrum defect migration in cubic ice. J. Phys. Chem. 88, 363–368 ( 1984).

    Article  CAS  Google Scholar 

  9. Wooldridge, P. J. & Devlin, J. P. Proton trapping and defect energetics in ice from FT-IR monitoring of photoinduced isotopic exchange of isolated D2O. J. Chem. Phys. 88, 3086– 3091 (1988).

    Article  ADS  CAS  Google Scholar 

  10. von Hipple, A., Runck, A. H. & Westphal, W. B. in Physics and Chemistry of Ice (eds Whalley, E., Jones, S. J. & Gold, L. W.) 236–241 (Royal Soc. Canada, Ottawa, (1973).

    Google Scholar 

  11. Tsekouras, A. A., Iedema, M. J., Ellison, G. B. & Cowin, J. P. Soft-landed ions: a route to ionic solution studies. Int. J. Mass Spectrom. Ion Proc. 174, 219–230 (1998).

    Article  ADS  CAS  Google Scholar 

  12. Kleyn, A. W. Ion-surface interactions — from channelling to soft-landing. Science 275, 1440–1441 ( 1997).

    Article  CAS  Google Scholar 

  13. Miller, S. A., Luo, H., Pachuta, S. J. & Cooks, R. G. Soft-landing of polyatomic ions at fluorinated self-assembled monolayer surfaces. Science 275, 1447–1450 (1997).

    Article  CAS  Google Scholar 

  14. Engelhardt, H. in Physics and Chemistry of Ice (eds Whalley, E., Jones, S. J. & Gold, L. W.) 226–235 (Royal Soc. Canada, Ottawa, (1973).

    Google Scholar 

  15. Pfeifer, R. & Hertz, H. G. Activation energies of the proton-exchange reactions in water measured with the 1H-NMR spin echo technique. Ber. Bunsenges. Phys. Chem. 94, 1349– 1355 (1990).

    Article  CAS  Google Scholar 

  16. Strongin, D. R., Mowlem, J. K., Lynne, K. G. & Kong, Y. Efficient magnetic focusing of low-energy ions (1–5 eV) onto solids for use in surface chemistry studies. Rev. Sci. Instrum. 63, 175–188 (1992).

    Article  ADS  CAS  Google Scholar 

  17. Tsekouras, A. A., Iedema, M. J. & Cowin, J. P. Soft-landed ion diffusion studies on vapor-deposited hexane films. J. Phys. Chem. (submitted).

  18. The KP5000 system (McAllister Technical Services, Coerd'Alen, Idaho 83815, US ).

  19. Materer, N. et al. Molecular surface structure of ice (0001): dynamical low-energy electron diffraction, total-energy calculations and molecular dynamics simulation. Surf. Sci. 381, 190–210 (1997).

    Article  ADS  CAS  Google Scholar 

  20. Tuckerman, M., Laasonen, K., Sprik, M. & Parrinello, M. Ab initio molecular dynamics simulation of the solvation and transport of hydronium and hydroxyl ions in water. J. Chem. Phys. 103, 150– 161 (1995).

    Article  ADS  CAS  Google Scholar 

  21. Kunst, M. & Warman, J. M. Nanosecond time-resolved conductivity studies of pulse ionized ice. 2. The mobility and trapping of protons. J. Phys. Chem. 87, 4093–4095 (1983).

    Article  CAS  Google Scholar 

  22. Johari, G. P. & Jones, S. J. Study of the low-temperature “transition” in ice 1 h by thermally stimulated depolarization measurements. J. Chem. Phys. 62, 4213–4223 (1975).

    Article  ADS  CAS  Google Scholar 

  23. Hermansson, K. & Ojamäe, L. On the role of electric fields for proton transfer in water. Solid State Ionics 77 , 34–42 (1995).

    Article  CAS  Google Scholar 

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Acknowledgements

We thank S. E. Barlow for advice. This work was conducted in the Environmental Molecular Sciences Laboratory, a collaborative users' facility of the US Department of Energy (DOE), under the Office of Biological and Environmental Research, and was supported by the Division of Chemical Sciences, US DOE. Pacific Northwest National Laboratory is operated by Battelle Memorial Institute for the US DOE.

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Authors and Affiliations

  1. Pacific Northwest National Laboratory , Box 999,MS K8-88, Richland, 99352, Washington , USA

    J. P. Cowin, M. J. Iedema & K. Wu

  2. Laboratory of Physical Chemistry, University of Athens, Athens, GR-15771, Greece

    A. A. Tsekouras

  3. Department of Chemistry & Biochemistry University of Colorado, Boulder, 80309, Colorado, USA

    G. B. Ellison

Authors
  1. J. P. Cowin
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  2. A. A. Tsekouras
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  3. M. J. Iedema
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  4. K. Wu
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  5. G. B. Ellison
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Correspondence to J. P. Cowin.

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Cowin, J., Tsekouras, A., Iedema, M. et al. Immobility of protons in ice from 30 to 190 K. Nature 398, 405–407 (1999). https://doi.org/10.1038/18848

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