Photochemical studies of unimolecular processes. II. Isomerization and quenching of vibrationally excited cycloheptatriene

Abstract

Experimental data on the thermal isomerizations of cycloheptatriene (CHT) and CHT-d 8 to toluene are used to calculate the rate constants for these isomerizations at different energies. Application to the photochemical studies reported in part I shows that quenching of vibrationally excited CHT is a multistep process, the average energies removed per collision (kJ/mol) being: CHT, 17 ± 5; toluene, 11 ± 5; SF 6 , 5.9 ± 0.9; CO 2 , 3.8 ± 0.4; He, 0.6 ± 0.1.