Spectroscopic snapshots of the proton-transfer mechanism in water

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Science  02 Dec 2016:
Vol. 354, Issue 6316, pp. 1131-1135
DOI: 10.1126/science.aaf8425

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Frame-by-frame view of acidic transport

Protons in acidic solution constantly hop from one water molecule to the next. In between the hopping, controversy lingers over the extent to which the proton either sticks largely to one water molecule in an Eigen motif or bridges two of them in a Zundel motif. It has been hard to probe this question directly because the distinguishing vibrational bands in bulk aqueous acid spectra are so broad. Wolke et al. studied deuterated prototypical Eigen clusters, D+(D2O)4, bound to an increasingly basic series of hydrogen bond acceptors (see the Perspective by Xantheas). These clusters displayed sharp bands in their vibrational spectra, highlighting a steadily evolving distortion toward a Zundel-like motif and pointing the way toward further investigations.

Science, this issue p. 1131; see also p. 1101


The Grotthuss mechanism explains the anomalously high proton mobility in water as a sequence of proton transfers along a hydrogen-bonded (H-bonded) network. However, the vibrational spectroscopic signatures of this process are masked by the diffuse nature of the key bands in bulk water. Here we report how the much simpler vibrational spectra of cold, composition-selected heavy water clusters, D+(D2O)n, can be exploited to capture clear markers that encode the collective reaction coordinate along the proton-transfer event. By complexing the solvated hydronium “Eigen” cluster [D3O+(D2O)3] with increasingly strong H-bond acceptor molecules (D2, N2, CO, and D2O), we are able to track the frequency of every O-D stretch vibration in the complex as the transferring hydron is incrementally pulled from the central hydronium to a neighboring water molecule.

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