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Hydrogen bonding at the water surface revealed by isotopic dilution spectroscopy

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.

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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.

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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.

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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.

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The authors declare no competing financial interests.

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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

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