Journal
SCIENCE
Volume 328, Issue 5981, Pages 1003-1005Publisher
AMER ASSOC ADVANCEMENT SCIENCE
DOI: 10.1126/science.1187707
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Funding
- U.S. Department of Energy Office of Basic Energy Sciences
- Carl Tryggers foundation
- Magnus Bergwall foundation
- Swedish Research Council
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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 NaClO(4) 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 degrees, in qualitative agreement with the jump angle observed in molecular dynamics simulations of the same aqueous NaClO(4) solution.
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