Photodissociation dynamics of the 2-methylallyl radical

Abstract

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-clusterab initio calculations.