Skip to main content

Thank you for visiting 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.

Ultrafast memory loss and energy redistribution in the hydrogen bond network of liquid H2O


Many of the unusual properties of liquid water are attributed to its unique structure, comprised of a random and fluctuating three-dimensional network of hydrogen bonds that link the highly polar water molecules1,2. One of the most direct probes of the dynamics of this network is the infrared spectrum of the OH stretching vibration3,4,5,6,7,8,9,10,11, which reflects the distribution of hydrogen-bonded structures and the intermolecular forces controlling the structural dynamics of the liquid. Indeed, water dynamics has been studied in detail5,6,7,8,9,10,11,12,13,14, most recently using multi-dimensional nonlinear infrared spectroscopy15,16 for acquiring structural and dynamical information on femtosecond timescales. But owing to technical difficulties, only OH stretching vibrations in D2O or OD vibrations in H2O could be monitored. Here we show that using a specially designed, ultrathin sample cell allows us to observe OH stretching vibrations in H2O. Under these fully resonant conditions, we observe hydrogen bond network dynamics more than one order of magnitude faster than seen in earlier studies that include an extremely fast sweep in the OH frequencies on a 50-fs timescale and an equally fast disappearance of the initial inhomogeneous distribution of sites. Our results highlight the efficiency of energy redistribution within the hydrogen-bonded network, and that liquid water essentially loses the memory of persistent correlations in its structure within 50 fs.

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

Relevant articles

Open Access articles citing this article.

Access options

Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Figure 1: Experimental set-up.
Figure 2: Spectrally integrated transient grating data in pure H2O.
Figure 3: Absorptive component of the spectrally resolved transient grating signal, plotted as a function of population time T.
Figure 4: Absorptive components of the two-dimensional-infrared echo spectra of pure liquid H2O for different population times.


  1. Eisenberg, D. & Kauzmann, W. The Structure and Properties of Water (Oxford Univ. Press, New York, 1969)

    Google Scholar 

  2. Franks, F. (ed.) Water, a Comprehensive Treatise (Plenum, New York, 1972)

  3. Luzar, A. & Chandler, D. Hydrogen-bond kinetics in liquid water. Nature 379, 55–57 (1996)

    Article  ADS  CAS  Google Scholar 

  4. Marx, D., Tuckerman, M. E., Hutter, J. & Parrinello, M. The nature of the hydrated excess proton in water. Nature 397, 601–604 (1999)

    Article  ADS  CAS  Google Scholar 

  5. Graener, H., Seifert, G. & Laubereau, A. New spectroscopy of water using tunable picosecond pulses in the infrared. Phys. Rev. Lett. 66, 2092–2095 (1991)

    Article  ADS  CAS  Google Scholar 

  6. Woutersen, S. & Bakker, H. J. Resonant intermolecular transfer of vibrational energy in liquid water. Nature 402, 507–509 (1999)

    Article  ADS  CAS  Google Scholar 

  7. Gale, G. M. et al. Femtosecond dynamics of hydrogen bonds in liquid water: A real-time study. Phys. Rev. Lett. 82, 1068–1071 (1999)

    Article  ADS  CAS  Google Scholar 

  8. Stenger, J., Madsen, D., Hamm, P., Nibbering, E. T. J. & Elsaesser, T. Ultrafast vibrational dephasing of liquid water. Phys. Rev. Lett. 87, 027401 (2001)

    Article  ADS  Google Scholar 

  9. Møller, K. B., Rey, R. & Hynes, J. T. Hydrogen bond dynamics in water and ultrafast infrared spectroscopy: a theoretical study. J. Phys. Chem. A 108, 1275–1289 (2004)

    Article  Google Scholar 

  10. Lawrence, C. P. & Skinner, J. L. Vibrational spectroscopy of HOD in liquid D2O. Infrared line shapes and vibrational Stokes shift. J. Chem. Phys. 117, 8847–8854 (2002)

    Article  ADS  CAS  Google Scholar 

  11. Torre, R., Bartolini, P. & Righini, R. Structural relaxation in supercooled water by time-resolved spectroscopy. Nature 428, 296–299 (2004)

    Article  ADS  CAS  Google Scholar 

  12. Asbury, J. B. et al. Water dynamics: vibrational echo correlation spectroscopy and comparison to molecular dynamics simulations. J. Phys. Chem. A 108, 1107–1119 (2004)

    Article  CAS  Google Scholar 

  13. Fecko, C. J., Eaves, J. D., Loparo, J. J., Tokmakoff, A. & Geissler, P. L. Ultrafast hydrogen-bond dynamics in the infrared spectroscopy of water. Science 301, 1698–1702 (2003)

    Article  ADS  CAS  Google Scholar 

  14. Stenger, J., Madsen, D., Hamm, P., Nibbering, E. T. J. & Elsaesser, T. A photon echo peak shift study of liquid water. J. Phys. Chem. A 106, 2341–2350 (2002)

    Article  CAS  Google Scholar 

  15. Asplund, M. C., Zanni, M. T. & Hochstrasser, R. M. Two dimensional infrared spectroscopy of peptides by phase-controlled femtosecond vibrational photon echoes. Proc. Natl Acad. Sci. USA 97, 8219–8224 (2000)

    Article  ADS  CAS  Google Scholar 

  16. Mukamel, S. Multidimensional femtosecond correlation spectroscopies of electronic and vibrational excitations. Annu. Rev. Phys. Chem. 51, 691–729 (2000)

    Article  ADS  CAS  Google Scholar 

  17. Cowan, M. L., Ogilvie, J. P. & Miller, R. J. D. Two-dimensional spectroscopy using diffractive optics based phased-locked photon echoes. Chem. Phys. Lett. 386, 184–189 (2004)

    Article  ADS  CAS  Google Scholar 

  18. Lepetit, L., Cheriaux, G. & Joffre, M. Linear techniques of phase measurement by femtosecond spectral interferometry for applications in spectroscopy. J. Opt. Soc. Am. B 104, 2467–2474 (1995)

    Article  ADS  Google Scholar 

  19. Hybl, J. D., Albrecht, A. W., Faeder, S. M. G. & Jonas, D. M. Two-dimensional electronic spectroscopy. Chem. Phys. Lett. 297, 307–313 (1998)

    Article  ADS  CAS  Google Scholar 

  20. Rice, S. A., Bergren, M. S., Beich, A. C. & Nielson, G. A theoretical analysis of the OH stretching spectra of ice Ih, liquid water, and amorphous solid water. J. Phys. Chem. 87, 4295–4308 (1983)

    Article  CAS  Google Scholar 

  21. Wojcik, M. J., Buch, V. & Devlin, J. P. Spectra of isotopic ice mixtures. J. Chem. Phys. 99, 2332–2344 (1993)

    Article  ADS  CAS  Google Scholar 

  22. Lock, A. J. & Bakker, H. J. Temperature dependence of vibrational relaxation in liquid H2O. J. Chem. Phys. 117, 1708–1713 (2002)

    Article  ADS  CAS  Google Scholar 

  23. Pakoulev, A., Wang, Z. & Dlott, D. Vibrational relaxation and spectral evolution following ultrafast OH stretch excitation of water. Chem. Phys. Lett. 371, 594–600 (2003)

    Article  ADS  CAS  Google Scholar 

  24. Jimenez, R., Fleming, G. R., Kumar, P. V. & Maroncelli, M. Femtosecond solvation dynamics in water. Nature 369, 471–473 (1994)

    Article  ADS  CAS  Google Scholar 

  25. Castner, E. W. Jr, Chang, Y. J., Chu, Y. C. & Walrafen, G. E. The intermolecular dynamics of liquid water. J. Chem. Phys. 102, 653–659 (1995)

    Article  ADS  CAS  Google Scholar 

  26. Saito, S. & Ohmine, I. Third order nonlinear response of liquid water. J. Chem. Phys. 106, 4889–4893 (1997)

    Article  ADS  CAS  Google Scholar 

  27. Pohorille, A., Pratt, L. R., LaViolette, R. A., Wilson, M. A. & MacElroy, R. D. Comparison of the structure of harmonic aequous glasses and liquid water. J. Chem. Phys. 87, 6070–6077 (1987)

    Article  ADS  CAS  Google Scholar 

  28. Poulsen, J. A., Nyman, G. & Nordholm, S. Wave packet study of ultrafast relaxation in ice Ih and liquid water. Resonant intermolecular vibrational energy transfer. J. Phys. Chem. A 107, 8420–8428 (2003)

    Article  CAS  Google Scholar 

Download references


We thank F. Weik for help with the use of a thermal imaging camera. Financial support by the Deutsche Forschungsgemeinschaft, the Humboldt foundation (R.J.D.M.), the Canadian Foundation for Innovation, the Natural Sciences and Engineering Research Council of Canada, and Photonics Research Ontario is acknowledged.

Author information

Authors and Affiliations


Corresponding author

Correspondence to R. J. D. Miller.

Ethics declarations

Competing interests

The authors declare that they have no competing financial interests.

Supplementary information

Supplementary Notes

This material describes control experiments illustrating the performance of our system. Supplementary Figure 1 illustrates the effects of isotopic substitution on the relaxation dynamics of liquid water. Supplementary Figure 2 shows that ultrathin Si3N4 windows eliminate nonlinear window signals. This file also contains additional references. (DOC 141 kb)

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Cowan, M., Bruner, B., Huse, N. et al. Ultrafast memory loss and energy redistribution in the hydrogen bond network of liquid H2O. Nature 434, 199–202 (2005).

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI:

This article is cited by


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.


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