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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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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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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DOI: https://doi.org/10.1038/18848
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