The loss of H· from vinyl alcohol radical cations. Comparison of theory and experiment

Loss of H· from ionised vinyl alcohol involves isomerisation into [CH3COH]+· followed by OH cleavage to produce CH3-C+O ions. The energy barrier for the reverse reaction, i.e. the thermoneutral ion radical recombination CH3-C+O + H· → [CH3COH]+·, was found to be 1.35±0.1 eV. This experimentally derived value is in excellent agreement with the results of recently published ab initio calculations at a high level of theory.