XVIth International Workshop on
Quantum Systems in
Chemistry and Physics
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Methylhydroxycarbene: Tunneling Control of a Chemical Reaction
Wesley D. Allen
Department of Chemistry, University of Georgia, Athens, Georgia, USA
Chemical reactivity is conventionally understood in broad terms of kinetic versus thermodynamic control, wherein the driving force is respectively the lowest activation barrier among the possible reaction paths or the lowest free energy of the final products. Here we expose quantum mechanical tunneling as a third driving force that can supersede traditional kinetic control and govern reactivity based on nonclassical penetration of the potential energy landscape intervening the reactants and products. These findings were afforded by the first experimental isolation and full spectroscopic and theoretical characterization of the elusive methylhydroxycarbene. Facile [1,2]hydrogen tunneling of methylhydroxycarbene to acetaldehyde occurs under a barrier of 28.0 kcal/mol with a half-life around 1 h, in preference to vinyl alcohol formation, which has a substantially lower barrier.


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