ChemInform Abstract: Dissociation of Cyclohexene and 1,4‐Cyclohexadiene in a Molecular Beam.

Abstract

Molecular‐beam photofragmentation translational spectroscopy of cyclohexene and 1,4‐cyclohexadiene was carried out using 193 nm and IR multiphoton excitation. At 193 nm, both the retro‐Diels–Alder reaction of cyclohexene and H2 elimination from both molecules were observed in the ground electronic state, indicating the occurrence of internal conversion from the initially excited electronic states. The retro‐Diels–Alder reaction is shown to be concerted up to an internal energy higher than 148 kcal/mol. Hydrogen‐atom elimination was also observed for both molecules following 193 nm excitation. The H atom is eliminated from an excited state of cyclohexene and is assigned to be from a carbon adjacent to the double bond, with a corresponding C–H bond energy of 87±3 kcal/mol. It is shown that the peak of the translational energy distribution for concerted dissociation in the ground state is determined mainly by the dynamics of the potential‐energy release along the reaction coordinate, and is not sensitive to either the amount of internal energy or the form of excitation.