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J Phys Chem A. 2007 Mar 22;111(11):2040-2. Epub 2007 Feb 23.

Hydrogen bonding between formic acid and water: complete stabilization of the intrinsically unstable conformer.

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Laboratory of Physical Chemistry, University of Helsinki, P.O. Box 55, FIN-00014 Helsinki, Finland.


We studied hydrogen bonding between formic acid (FA) and water in solid argon and identified the first water complex with the higher-energy conformer cis-FA. In sharp contrast to cis-FA monomer, cis-FA interacting with water is very stable at low temperatures, which was explained by strong O-H...O hydrogen bonding. These benchmark results show that hydrogen bonding can terminate proton tunneling reactions and efficiently stabilize intrinsically unstable conformational structures in complex asymmetrical hydrogen-bonded networks. This general effect occurs when the energy difference between conformers is smaller than the hydrogen bond interaction energy, which opens perspectives in chemistry on intrinsically unstable conformers.

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