Roaming Radical Pathways for the Decomposition of Alkanes

CASPT2 calculations predict the existence of roaming radical pathways for the decomposition of propane, n-butane, isobutane and neopentane. The roaming radical paths lead to the formation of an alkane and an alkene instead of the expected radical products. The predicted barriers for the roaming radical paths lie similar to 1 kcal/mol below the corresponding radical asymptotes.