Skip to main content

Thank you for visiting nature.com. 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.

  • Letter
  • Published:

Hydrogen bonding at the water surface revealed by isotopic dilution spectroscopy

Nature volume 474, pages 192–195 (2011)Cite this article

Subjects

Abstract

The air–water interface is perhaps the most common liquid interface. It covers more than 70 per cent of the Earth’s surface and strongly affects atmospheric, aerosol and environmental chemistry. The air–water interface has also attracted much interest as a model system that allows rigorous tests of theory, with one fundamental question being just how thin it is. Theoretical studies have suggested a surprisingly short ‘healing length’ of about 3 ångströms (1 Å = 0.1 nm), with the bulk-phase properties of water recovered within the top few monolayers1,2,3. However, direct experimental evidence has been elusive owing to the difficulty of depth-profiling the liquid surface on the ångström scale. Most physical, chemical and biological properties of water, such as viscosity, solvation, wetting and the hydrophobic effect, are determined by its hydrogen-bond network. This can be probed by observing the lineshape of the OH-stretch mode, the frequency shift of which is related to the hydrogen-bond strength4,5,6. Here we report a combined experimental and theoretical study of the air–water interface using surface-selective heterodyne-detected vibrational sum frequency spectroscopy to focus on the ‘free OD’ transition found only in the topmost water layer. By using deuterated water and isotopic dilution to reveal the vibrational coupling mechanism, we find that the free OD stretch is affected only by intramolecular coupling to the stretching of the other OD group on the same molecule. The other OD stretch frequency indicates the strength of one of the first hydrogen bonds encountered at the surface; this is the donor hydrogen bond of the water molecule straddling the interface, which we find to be only slightly weaker than bulk-phase water hydrogen bonds. We infer from this observation a remarkably fast onset of bulk-phase behaviour on crossing from the air into the water phase.

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

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Figure 1: The vibrational coupling scheme of the free OD stretch at the air–water interface.
Figure 2: The spectra of the free OD stretch at the air–water interface.
Figure 3: Changes in vibrational spectra with isotopic dilution.
Figure 4: Simulating and modelling the air–water interface.

Similar content being viewed by others

References

  1. Townsend, R. M., Gryko, J. & Rice, S. A. Structure of the liquid vapor interface of water. J. Chem. Phys. 82, 4391–4392 (1985)

    Article  ADS  CAS  Google Scholar 

  2. Morita, A. & Hynes, J. T. A theoretical analysis of the sum frequency generation spectrum of the water surface. Chem. Phys. 258, 371–390 (2000)

    Article  CAS  Google Scholar 

  3. Taylor, R. S., Dang, L. X. & Garrett, B. C. Molecular dynamics simulations of the liquid/vapor interface of SPC/E water. J. Phys. Chem. 100, 11720–11725 (1996)

    Article  CAS  Google Scholar 

  4. Rey, R., Moller, K. B. & Hynes, J. T. Hydrogen bond dynamics in water and ultrafast infrared spectroscopy. J. Phys. Chem. A 106, 11993–11996 (2002)

    Article  CAS  Google Scholar 

  5. Lawrence, C. P. & Skinner, J. L. Ultrafast infrared spectroscopy probes hydrogen-bonding dynamics in liquid water. Chem. Phys. Lett. 369, 472–477 (2003)

    Article  ADS  CAS  Google Scholar 

  6. 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 

  7. Richmond, G. L. Molecular bonding and interactions at aqueous surfaces as probed by vibrational sum frequency spectroscopy. Chem. Rev. 102, 2693–2724 (2002)

    Article  CAS  Google Scholar 

  8. Ostroverkhov, V., Waychunas, G. A. & Shen, Y. R. New information on water interfacial structure revealed by phase-sensitive surface spectroscopy. Phys. Rev. Lett. 94, 046102 (2005)

    Article  ADS  Google Scholar 

  9. Sovago, M., Campen, R. K., Bakker, H. J. & Bonn, M. Hydrogen bonding strength of interfacial water determined with surface sum-frequency generation. Chem. Phys. Lett. 470, 7–12 (2009)

    Article  ADS  CAS  Google Scholar 

  10. Stiopkin, I. V., Jayathilake, H. D., Bordenyuk, A. N. & Benderskii, A. V. Heterodyne-detected vibrational sum frequency generation spectroscopy. J. Am. Chem. Soc. 130, 2271–2275 (2008)

    Article  CAS  Google Scholar 

  11. Gan, W., Wu, D., Zhang, Z., Feng, R. R. & Wang, H. F. Polarization and experimental configuration analyses of sum frequency generation vibrational spectra, structure, and orientational motion of the air/water interface. J. Chem. Phys. 124, 114705 (2006)

    Article  ADS  Google Scholar 

  12. Nihonyanagi, S., Yamaguchi, S. & Tahara, T. Direct evidence for orientational flip-flop of water molecules at charged interfaces: a heterodyne-detected vibrational sum frequency generation study. J. Chem. Phys. 130, 204704 (2009)

    Article  ADS  Google Scholar 

  13. Auer, B. M. & Skinner, J. L. Vibrational sum-frequency spectroscopy of the liquid/vapor interface for dilute HOD in D2O. J. Chem. Phys. 129, 214705 (2008)

    Article  ADS  CAS  Google Scholar 

  14. Corcelli, S. A., Lawrence, C. P. & Skinner, J. L. Combined electronic structure/molecular dynamics approach for ultrafast infrared spectroscopy of dilute HOD in liquid H2O and D2O. J. Chem. Phys. 120, 8107–8117 (2004)

    Article  ADS  CAS  Google Scholar 

  15. Nagata, Y. & Mukamel, S. Vibrational sum-frequency generation spectroscopy at the water/lipid interface: molecular dynamics simulation study. J. Am. Chem. Soc. 132, 6434–6442 (2010)

    Article  CAS  Google Scholar 

  16. Ishiyama, T. & Morita, A. Vibrational spectroscopic response of intermolecular orientational correlation at the water surface. J. Phys. Chem. C 113, 16299–16302 (2009)

    Article  CAS  Google Scholar 

  17. Du, Q., Superfine, R., Freysz, E. & Shen, Y. R. Vibrational spectroscopy of water at the vapor water interface. Phys. Rev. Lett. 70, 2313–2316 (1993)

    Article  ADS  CAS  Google Scholar 

  18. Du, Q., Freysz, E. & Shen, Y. R. Surface vibrational spectroscopic studies of hydrogen-bonding and hydrophobicity. Science 264, 826–828 (1994)

    Article  ADS  CAS  Google Scholar 

  19. Skinner, J. L., Auer, B. M. & Lin, Y. S. Vibrational line shapes, spectral diffusion, and hydrogen bonding in liquid water. Adv. Chem. Phys. 142, 59–103 (2009)

    CAS  Google Scholar 

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

    Article  ADS  CAS  Google Scholar 

  21. Raymond, E. A., Tarbuck, T. L., Brown, M. G. & Richmond, G. L. Hydrogen-bonding interactions at the vapor/water interface investigated by vibrational sum-frequency spectroscopy of HOD/H2O/D2O mixtures and molecular dynamics simulations. J. Phys. Chem. B 107, 546–556 (2003)

    Article  CAS  Google Scholar 

  22. Tian, C. S. & Shen, Y. R. Isotopic dilution study of the water/vapor interface by phase-sensitive sum-frequency vibrational spectroscopy. J. Am. Chem. Soc. 131, 2790–2791 (2009)

    Article  CAS  Google Scholar 

  23. Lepetit, L., Cheriaux, G. & Joffre, M. Linear techniques of phase measurement by femtosecond spectral interferometry for applications in spectroscopy. J. Opt. Soc. Am. B 12, 2467–2474 (1995)

    Article  ADS  CAS  Google Scholar 

  24. Stiopkin, I. V., Jayathilake, H. D., Weeraman, C. & Benderskii, A. V. Temporal effects on spectroscopic line shapes, resolution, and sensitivity of the broad-band sum frequency generation. J. Chem. Phys. 132, 234503 (2010)

    Article  ADS  Google Scholar 

  25. Shimanouchi, T. Tables of Molecular Vibrational Frequencies Consolidated Vol. I (National Bureau of Standards, 1972)

    Google Scholar 

  26. Auer, B. M. & Skinner, J. L. Vibrational sum-frequency spectroscopy of the water liquid/vapor interface. J. Phys. Chem. B 113, 4125–4130 (2009)

    Article  CAS  Google Scholar 

  27. Corcelli, S. A. & Skinner, J. L. Infrared and Raman line shapes of dilute HOD in liquid H2O and D2O from 10 to 90 degrees C. J. Phys. Chem. A 109, 6154–6165 (2005)

    Article  CAS  Google Scholar 

  28. Loparo, J. J., Roberts, S. T., Nicodemus, R. A. & Tokmakoff, A. Variation of the transition dipole moment across the OH stretching band of water. Chem. Phys. 341, 218–229 (2007)

    Article  CAS  Google Scholar 

  29. Barker, E. F. & Sleator, W. W. The infrared spectrum of heavy water. J. Chem. Phys. 3, 660–663 (1935)

    Article  ADS  CAS  Google Scholar 

  30. Max, J. J. & Chapados, C. Isotope effects in liquid water by infrared spectroscopy. J. Chem. Phys. 116, 4626–4642 (2002)

    Article  ADS  CAS  Google Scholar 

Download references

Acknowledgements

The experiments presented here were supported by the NSF CAREER grant number CHE-0449720 (I.V.S., C.W., F.Y.S. and A.V.B.). J.L.S. thanks the NSF and the DOE for support from grants CHE-0750307 and DE-FG02-09ER16110, respectively.

Author information

Author notes

  1. Igor V. Stiopkin, Champika Weeraman & Fadel Y. Shalhout

    Present address: Present addresses: Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53705, USA (I.V.S.); Steacie Institute for Molecular Sciences, National Research Council, Ottawa, Ontario, K1A OR6 Canada (C.W.); Department of Chemistry, University of Southern California, Los Angeles, California 90089, USA (F.Y.S. and A.V.B.).,

Authors and Affiliations

  1. Department of Chemistry, Wayne State University, Detroit, 48202, Michigan, USA

    Igor V. Stiopkin, Champika Weeraman, Fadel Y. Shalhout & Alexander V. Benderskii

  2. Department of Chemistry, University of Wisconsin-Madison, Madison, 53705, Wisconsin, USA

    Piotr A. Pieniazek & James L. Skinner

Authors
  1. Igor V. Stiopkin
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Champika Weeraman
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Piotr A. Pieniazek
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Fadel Y. Shalhout
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. James L. Skinner
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Alexander V. Benderskii
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

I.V.S., C.W., F.Y.S. and A.V.B. constructed the spectroscopic set-up, executed the experiments, and performed the analysis of the spectroscopic data. P.A.P. and J.L.S. carried out molecular dynamics simulations and calculation of the spectra. All authors discussed the results and contributed to the preparation of the manuscript.

Corresponding author

Correspondence to Alexander V. Benderskii.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

The file contains Supplementary Text, Supplementary Figures 1-5 with legends and additional references. (PDF 851 kb)

PowerPoint slides

Rights and permissions

Reprints and permissions

About this article

Cite this article

Stiopkin, I., Weeraman, C., Pieniazek, P. et al. Hydrogen bonding at the water surface revealed by isotopic dilution spectroscopy. Nature 474, 192–195 (2011). https://doi.org/10.1038/nature10173

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature10173

This article is cited by

Comments

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.

Search

Advanced search

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