Ultrafast vibrational energy transfer at the water/air interface revealed by two-dimensional surface

Abstract

Water is very different from liquids of similar molecular weight, and one of its unique properties is the very efficient transfer of vibrational energy between molecules, which arises as a result of strong dipole–dipole interactions between the O–H oscillators. Although we have a sound understanding of such energy transfer in bulk water, we know less about how, and how quickly, transfer occurs at its interface with a hydrophobic phase, because specifically addressing the outermost monolayer is difficult. Here, we use ultrafast two-dimensional surface-specific vibrational spectroscopy to probe the interfacial energy dynamics of heavy water (D2O) at the water/air interface. The measurements reveal the presence of surprisingly rapid energy transfer, both between hydrogen-bonded interfacial water molecules (intermolecular), and between O–D groups sticking out from the water surface and those located on the same molecule and pointing towards the water bulk (intramolecular). Vibrational energy transfer occurs on sub-picosecond timescales, and its rates and pathways can be quantified directly. At water's surface, its network of hydrogen-bonds is abruptly interrupted, conferring distinct properties on interfacial water from bulk water. Understanding aqueous interfaces is essential for many environmental, technological and biophysical systems, and now the pathways and rates of energy transfer at the water/air interface are elucidated using a surface-specific ultrafast spectroscopic technique.

Cite this article

Zhang, Z., Piatkowski, L., Bakker, H. et al. Ultrafast vibrational energy transfer at the water/air interface revealed by two-dimensional surface vibrational spectroscopy. Nature Chem 3, 888–893 (2011). https://doi.org/10.1038/nchem.1158

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