Effective potential of β-bonds in free radicals

Abstract

An empirical potential energy function which incorporates π-bonding explicitly is able to quantitatively account for the observed stretching frequencies of β bonds in free radicals and the activation energies of their fission with only one adjustable parameter. This approach unifies the overall dynamic behavior of bonds leading to (1) the prediction of stretching frequencies from kinetic and thermochemical data and (2) the location of transition states for radical decomposition and disproportionation reactions in a self-consistent way. The cases of alkyl, formyl, hydroperoxyl, and hydroxycarbonyl radicals are analyzed.

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