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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.

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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.

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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.

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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).

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