Photodissociation dynamics of the 2-methylallyl radical

Time- and frequency-resolved photoionization of the hydrogen atom product from a jet-cooled electronically excited 2-methylallyl radical, C4H7, provides information on the dissociation dynamics. The measured dissociation rates and kinetic energy release of 2-methylallyl and its isotopologue CD3C3H4 combined with high level ab initio calculations suggests unimolecular dissociation with methylenecyclopropane and hydrogen as the major C-H bond fission channel with no evidence for nonstatistical behavior in dissociation. Other possible dissociation and isomerization pathways are discussed based on the results of the coupled-cluster ab initio calculations.