Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

The interatomic structure of water at supercritical temperatures

Abstract

LIQUID water, the medium in which life both began and persists, is in many ways a most unusual fluid. Much is known about the macroscopic properties of the condensed and gaseous states of water, but our understanding of the microscopic forces that define water structure remains incomplete1. This structure, described in terms of correlations between the pairs of atoms O–H, O–O and H–H (ref. 2), can be studied by neutron diffraction techniques involving isotopic substitution3. In particular, the signature of hydrogen bonding is apparent in neutron diffraction experiments as a peak in the pair correlation function of O and H (gOH (r)) at about 1.9 Å (refs 3, 4). Here we extend such studies into the supercritical regime of water, in which there is no longer any distinction between the liquid and vapour phases. We find that at the supercritical temperature of 400 °C almost all hydrogen bonding is broken down, even though the thermal energy kBT is considerably less than the energy of the hydrogen bond. Our results are markedly different from the predictions of computer simulations under comparable conditions5 using a common model of water5–7. Our results provide a sensitive test of models of water structure more generally, and give some indication of the environment that solute molecules will experience in extraction and reaction processes that employ supercritical water as a solvent8.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Prices may be subject to local taxes which are calculated during checkout

Similar content being viewed by others

References

  1. Neilson, G. W. & Enderby, J. E. (eds) Water and Aqueous Solutions (Adam Hilger, Bristol, 1986).

  2. Soper, A. K. & Phillips, M. G. Chem. Phys. 107, 47–60 (1986).

    Article  CAS  Google Scholar 

  3. Enderby, J. E. & Neilson, G. W. in Water, A Comprehensive Treatise Vol. 1 (ed. Franks, F.) Ch. 1 (Plenum, New York, 1979).

    Google Scholar 

  4. Yamaguchi, T. & Soper, A. K. ISIS Annual Report No. A110, Report No. 91-050, Vol. 2 (Rutherford Appleton Laboratory, Chilton, 1991).

  5. Cummings, P. T., Cochran, H. D., Samonson, J. M., Mesmer, R. E. & Karaboni, S. J. Chem. Phys. 94, 5606–5621 (1991).

    Article  ADS  CAS  Google Scholar 

  6. Mountain, R. D., J. chem. Phys. 90, 1866–1870 (1989).

    Article  ADS  CAS  Google Scholar 

  7. Guissani, Y. & Guillot, B. J. chem. Phys. 98, 8221–8235 (1993).

    Article  ADS  CAS  Google Scholar 

  8. Pichal, M. & Sifner, O. (eds) Properties of Water and Steam (Hemisphere, New York, 1989).

  9. Stillinger, F. H. & Rahman, A. J. chem. Phys. 60, 1545–1557 (1974).

    Article  ADS  CAS  Google Scholar 

  10. Corongiu, G. & Clementi, E. J. chem. Phys. 97, 2030–2038 (1992); 98, 2241–2249 (1993).

    Article  ADS  CAS  Google Scholar 

  11. Impey, R. W., Klein, M. C. & McDonald, I. R. J. chem. Phys. 74, 647–652 (1981).

    Article  ADS  CAS  Google Scholar 

  12. Ferrario, M. & Tani, A. Chem. Phys. Lett. 121, 182–186 (1985).

    Article  ADS  CAS  Google Scholar 

  13. Neilson, G. W., Broadbent, R., Howe, M. A. & Frank, E. U. in Properties of Water and Steam (eds Pichal, M. & Sifner, O.) 335–346 (Hemisphere, New York, 1989).

    Google Scholar 

  14. Soper, A. K. & Turner, J. Int. J. mod. Phys. 7, 3049–3076 (1993).

    Article  ADS  CAS  Google Scholar 

  15. Soper, A. K., Howells, W. S. & Hannon, A. C. Report No. 89-046 (Rutherford Appleton Laboratory, Chilton, 1989).

  16. Walrafen, G. E., Fisher, M. R., Hokmabadi, M. S. & Yang, W-H., J. chem. Phys. 85, 6970–6982 (1986).

    Article  ADS  CAS  Google Scholar 

  17. Luzar, A. J. chem. Phys. 91, 3603–3613 (1989).

    Article  ADS  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Rights and permissions

Reprints and permissions

About this article

Cite this article

Postorino, P., Tromp, R., Ricci, MA. et al. The interatomic structure of water at supercritical temperatures. Nature 366, 668–670 (1993). https://doi.org/10.1038/366668a0

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1038/366668a0

This article is cited by

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.

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing