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

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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.

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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. 1

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

  2. 2

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

  3. 3

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

  4. 4

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

  5. 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)

  6. 6

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

  7. 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)

  8. 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)

  9. 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)

  10. 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)

  11. 11

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

  12. 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)

  13. 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)

  14. 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)

  15. 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)

  16. 16

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

  17. 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)

  18. 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)

  19. 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)

  20. 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)

  21. 21

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

  22. 22

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

  23. 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)

  24. 24

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

  25. 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)

  26. 26

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

  27. 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)

  28. 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)

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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.

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Correspondence to R. J. D. Miller.

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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)

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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) doi:10.1038/nature03383

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