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Large Angular Jump Mechanism Observed for Hydrogen Bond Exchange in Aqueous Perchlorate Solution

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Science  21 May 2010:
Vol. 328, Issue 5981, pp. 1003-1005
DOI: 10.1126/science.1187707

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Abstract

The mechanism for hydrogen bond (H-bond) switching in solution has remained subject to debate despite extensive experimental and theoretical studies. We have applied polarization-selective multidimensional vibrational spectroscopy to investigate the H-bond exchange mechanism in aqueous NaClO4 solution. The results show that a water molecule shifts its donated H-bonds between water and perchlorate acceptors by means of large, prompt angular rotation. Using a jump-exchange kinetic model, we extracted an average jump angle of 49 ± 4°, in qualitative agreement with the jump angle observed in molecular dynamics simulations of the same aqueous NaClO4 solution.

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