Ultrafast 2D IR spectroscopy of the excess proton in liquid water

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Science  02 Oct 2015:
Vol. 350, Issue 6256, pp. 78-82
DOI: 10.1126/science.aab3908

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How well does water share its protons?

Chemists have spent centuries trying to understand what acids look like at the molecular level. It's clear now that water molecules in the liquid accommodate extra protons. Less clear is whether the protons piggyback on individual water molecules (Eigen structure) or find shared accommodation between two at a time (Zundel structure). Thämer et al. acquired time-resolved vibrational spectra across an unusually broad span of the mid-infrared, allowing them to monitor stretches and bends at the same time. Their results imply a more prominent role for the Zundel structure than previously anticipated.

Science, this issue p. 78


Despite decades of study, the structures adopted to accommodate an excess proton in water and the mechanism by which they interconvert remain elusive. We used ultrafast two-dimensional infrared (2D IR) spectroscopy to investigate protons in aqueous hydrochloric acid solutions. By exciting O–H stretching vibrations and detecting the spectral response throughout the mid-IR region, we observed the interaction between the stretching and bending vibrations characteristic of the flanking waters of the Zundel complex, [H(H2O)2]+, at 3200 and 1760 cm−1, respectively. From time-dependent shifts of the stretch-bend cross peak, we determined a lower limit on the lifetime of this complex of 480 femtoseconds. These results suggest a key role for the Zundel complex in aqueous proton transfer.

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