Simple Marcus-Theory-Type Model for Hydrogen-Atom Transfer/Proton-Coupled Electron Transfer
The Journal of Physical Chemistry Letters2011Vol. 2(12), pp. 1481–1489
Citations Over TimeTop 10% of 2011 papers
Abstract
Hydrogen atom transfer reactions are the simplest class of proton-coupled electron transfer (PCET) processes. These reactions involve transfer of one electron and one proton from one reagent to another, in the same kinetic step: XH + Y → X + HY. A predictive model for these reactions based on the Marcus cross relation is described. The model predicts rate constants within one or two orders of magnitude in most cases, over a very wide range of reactants and solvents. This remarkable result implies a surprising generality of the additivity postulate for the reaction intrinsic barriers, and a smaller role for the quantum mechanical details of the proton and electron transfers.
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