Delocalization of Protons in Liquid Water
10.1126/science.1073298
Crossref journal-article
American Association for the Advancement of Science (AAAS)
Science (221)
Abstract

We find that the vibrational potential of the O-H stretch vibrations of liquid water shows extreme anharmonicity that arises from the O-H ⋯ O hydrogen bond interaction. We observe that already in the second excited state of the O-H stretch vibration, the hydrogen atom becomes delocalized between the oxygen atoms of two neighboring water molecules. The energy required for this delocalization is unexpectedly low and corresponds to less than 20% of the dissociation energy of the O-H bond of the water molecule in the gas phase.

Bibliography

Bakker, H. J., & Nienhuys, H.-K. (2002). Delocalization of Protons in Liquid Water. Science, 297(5581), 587–590.

Authors 2
  1. H. J. Bakker (first)
  2. H.-K. Nienhuys (additional)
References 27 Referenced 123
  1. de Grotthuss C. J. T., Ann. Chim. 58, 54 (1806). / Ann. Chim. by de Grotthuss C. J. T. (1806)
  2. 10.1063/1.469654
  3. ___, J. Phys. Chem. 99, 5749 (1995). (10.1021/j100016a003) / J. Phys. Chem. by ___ (1995)
  4. 10.1038/17579
  5. Lock A., Woutersen S., Bakker H. J., J. Phys. Chem. A 105, 1238 (2001). (10.1021/jp003158e) / J. Phys. Chem. A by Lock A. (2001)
  6. 10.1103/PhysRevLett.81.1106
  7. Deak J., Rhea S., Iwaki L., Dlott D., J. Phys. Chem. A104, 4866 (2000). (10.1021/jp994492h) / J. Phys. Chem. by Deak J. (2000)
  8. 10.1126/science.278.5338.658
  9. Laenen R., Rauscher C., Laubereau A., Phys. Rev. Lett. 80, 2622 (1998). (10.1103/PhysRevLett.80.2622) / Phys. Rev. Lett. by Laenen R. (1998)
  10. Gale G. M., Gallot G., Hache F., Lascoux N., Bratos S., Leicknam J.-C., Phys. Rev. Lett. 82, 1086 (1999). / Phys. Rev. Lett. by Gale G. M. (1999)
  11. Woutersen S., Bakker H. J., Phys. Rev. Lett. 83, 2077 (1999). (10.1103/PhysRevLett.83.2077) / Phys. Rev. Lett. by Woutersen S. (1999)
  12. ___, Nature 402, 507 (1999). (10.1038/990058) / Nature by ___ (1999)
  13. Independently tunable mid-IR pump and probe pulses are generated through parametric amplification processes in β-barium borate (BBO) and potassium titanyl phosphate (KTP) crystals that are pumped by the pulses (800 nm 100 fs 3 mJ 1 kHz) delivered by a Ti:sapphire regenerative amplifier. The generated mid-IR pulses are tunable between 2.7 and 4 μm (2500 to 3700 cm −1 ); they have a pulse duration of 200 fs and an energy per pulse of 20 μJ (pump) and 2 μJ (probe). The pump and probe pulses are focused to a common focal spot with a diameter of ∼100 μm in the sample.
  14. Graener H., Seifert G., J. Chem. Phys. 98, 36 (1993). (10.1063/1.464629) / J. Chem. Phys. by Graener H. (1993)
  15. Lippincott E. R., Schroeder R., J. Chem. Phys. 23, 1099 (1955). (10.1063/1.1742196) / J. Chem. Phys. by Lippincott E. R. (1955)
  16. F. Franks Ed. Water a Comprehensive Treatise (Plenum New York 1972).
  17. G. Dahlquist A. Björck N. Anderson Numerical Methods (Prentice-Hall Englewood Cliffs NJ 1974).
  18. Novak A., Struct. Bonding (Berlin) 18, 177 (1974). (10.1007/BFb0116438) / Struct. Bonding (Berlin) by Novak A. (1974)
  19. 10.1016/0022-2860(86)87054-5
  20. The transient spectrum at a particular delay was calculated by multiplying the time-dependent excited distributions in the potentials W 0 ( R ) and W 1 ( R ) with the R -dependent transition probabilities of the v = 0 → 1 and v = 1 → 2 transitions. These distributions were then translated into frequency-dependent functions by using the relations between R and the transition frequencies [ W 1 ( R ) − W 0 ( R )]/ h and [ W 2 ( R ) − W 1 ( R )]/ h. To obtain the final calculated transient spectrum the v = 0 → 1 bleaching the v = 1 → 0 stimulated emission and the v = 1 → 2 induced absorption contributions were added and convolved with the probe spectrum and the homogeneous broadening.
  21. Stenger J., Madsen D., Hamm P., Nibbering E. T. J., Elsaesser T., Phys. Rev. Lett. 87, 027401 (2001). (10.1103/PhysRevLett.87.027401) / Phys. Rev. Lett. by Stenger J. (2001)
  22. R. Kubo M. Toda N. Hashitsume Statistical Physics II Nonequilibrium Statistical Mechanics (Springer Berlin 1995).
  23. Luck W. A. P., Wess T., Can. J. Chem. 69, 1819 (1991). (10.1139/v91-266) / Can. J. Chem. by Luck W. A. P. (1991)
  24. 10.1126/science.1056991
  25. P. W. Atkins Physical Chemistry (Oxford Univ. Press Oxford ed. 6 1998).
  26. 10.1021/j100258a035
  27. We thank D. Frenkel for useful discussions. The research presented in this paper is part of the research program of the Stichting Fundamenteel Onderzoek der Materie (Foundation for Fundamental Research on Matter) and was made possible by financial support from the Nederlandse Organisatie voor Wetenschappelijk Onderzoek (Netherlands Organization for the Advancement of Research).
Dates
Type When
Created 22 years, 10 months ago (Oct. 1, 2002, 3:34 p.m.)
Deposited 1 year, 7 months ago (Jan. 9, 2024, 9:52 p.m.)
Indexed 1 year, 2 months ago (June 9, 2024, 12:09 p.m.)
Issued 23 years, 1 month ago (July 26, 2002)
Published 23 years, 1 month ago (July 26, 2002)
Published Print 23 years, 1 month ago (July 26, 2002)
Funders 0

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@article{Bakker_2002, title={Delocalization of Protons in Liquid Water}, volume={297}, ISSN={1095-9203}, url={http://dx.doi.org/10.1126/science.1073298}, DOI={10.1126/science.1073298}, number={5581}, journal={Science}, publisher={American Association for the Advancement of Science (AAAS)}, author={Bakker, H. J. and Nienhuys, H.-K.}, year={2002}, month=jul, pages={587–590} }