Resonant intermolecular transfer of vibrational energy in liquid water

Article metrics


Many biological, chemical and physical processes involve the transfer of energy. In the case of electronic excitations, transfer between molecules is rapid, whereas for vibrations in the condensed phase, resonant energy transfer is an unlikely process because the typical timescale of vibrational relaxation (a few picoseconds) is much shorter than that of resonant intermolecular vibrational energy transfer1,2. For the OH-stretch vibration in liquid water, which is of particular importance due to its coupling to the hydrogen bond, extensive investigations have shown that vibrational relaxation takes place with a time constant of 740 ± 25 femtoseconds (ref. 7). So for resonant intermolecular energy transfer to occur in liquid water, the interaction between the OH-stretch modes of different water molecules needs to be extremely strong. Here we report time-resolved pump-probe laser spectroscopy measurements that reveal the occurrence of fast resonant intermolecular transfer of OH-stretch excitations over many water molecules before the excitation energy is dissipated. We find that the transfer process is mediated by dipole–dipole interactions (the Förster transfer mechanism9) and additional mechanisms that are possibly based on intermolecular anharmonic interactions involving hydrogen bonds. Our findings suggest that liquid water may play an important role in transporting vibrational energy between OH groups located on either different biomolecules or along extended biological structures. OH groups in a hydrophobic environment should accordingly be able to remain in a vibrationally excited state longer than OH groups in a hydrophilic environment.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Figure 1: Rotational anisotropy R(τ)/R(0) as a function of delay.


  1. 1

    Vlahoyannis,Y. P., Krueger,H., Knudtson,J. T. & Weitz,E. Vibration-vibration energy transfer processes in liquid xenon: a measurement of the rate constant for HCl(v = 2) + HCl(v = 0) → 2HCl(v = 1). Chem. Phys. Lett. 121, 272–278 (1985).

  2. 2

    Apkarian,V. A., Wiedeman,L., Janiesch,W. & Weitz,E. Vibrational energy transfer and migration processes in matrix isolated CH3F. J. Chem. Phys. 85, 5593–5610 (1986).

  3. 3

    Hadz̆i,D. & Bratos,S. in The Hydrogen Bond (eds Schuster, P., Zundel, G. & Sandorfy, C.) Vol. II, Ch. 12 (Elsevier, Amsterdam, 1976).

  4. 4

    Woutersen,S., Emmerichs,U. & Bakker,H. J. Femtosecond mid-infrared pump-probe spectroscopy of liquid water: evidence for a two-component structure. Science 278, 658–660 (1997).

  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

    Laenen,R., Rauscher,C. & Laubereau,A. Dynamics of local substructures in water observed by ultrafast infrared hole burning. Phys. Rev. Lett. 80, 2622–2625 (1998).

  7. 7

    Woutersen,S., Emmerichs,U., Nienhuys,H.-K. & Bakker,H. J. Anomalous temperature dependence of vibrational lifetimes in water and ice. Phys. Rev. Lett. 81, 1106–1109 (1998).

  8. 8

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

  9. 9

    Förster,T. in Modern Quantum Chemistry Vol. III (ed. Sinanoǧlu, O.) 93–137 (Academic, New York, 1965).

  10. 10

    Emmerichs,U., Woutersen,S. & Bakker,H. J. Generation of intense femtosecond optical pulses around 3 µm with kHz rep-rate. J. Opt. Soc. Am. B 14, 1480–1483 (1997).

  11. 11

    Graener,H., Seifert,G. & Laubereau,A. Direct observation of rotational relaxation times by time-resolved infrared spectroscopy. Chem. Phys. Lett. 172, 435–439 (1990).

  12. 12

    Nienhuys,H.-K., Woutersen,S., van Santen,R. A. & Bakker,H. J. Mechanism for vibrational relaxation in water investigated by femtosecond infrared spectroscopy. J. Chem. Phys. 111, 1494–1500 (1999).

  13. 13

    Stepanov,B. I. Interpretation of the regularities in the spectra of molecules forming the intermolecular hydrogen bond by the predissociation effect. Nature 157, 808 (1946).

  14. 14

    Staib,A. & Hynes,J. T. Vibrational predissociation in hydrogen-bonded OHO complexes via OH stretch–OO stretch energy transfer. Chem. Phys. Lett. 204, 197–205 (1993).

  15. 15

    Eisenthal,K. B. Measurement of intermolecular energy transfer using picosecond light pulses. Chem. Phys. Lett. 6, 155–157 (1970).

  16. 16

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

  17. 17

    Rønne,C., Åstrand,P.-O. & Keiding,S. THz spectroscopy of liquid H2O and D2O. Phys. Rev. Lett. 82, 2888–2891 (1999).

  18. 18

    Szabo,A. Theory of fluorescence depolarization in macromolecules and membranes. J. Chem. Phys. 81, 150–167 (1984).

Download references


We thank H. Schoenmaker for technical support and W. van der Zande and P. van der Meulen for critically reading the manuscript. This work is part of the research programme of the “Stichting voor Fundamenteel Onderzoek der Materie” (FOM), which is financially supported by the “Nederlandse organisatie voor Wetenschappelijke Onderzoek” (NWO).

Author information

Correspondence to Sander Woutersen.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Woutersen, S., Bakker, H. Resonant intermolecular transfer of vibrational energy in liquid water. Nature 402, 507–509 (1999) doi:10.1038/990058

Download citation

Further reading


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.