UNIMOLECULAR PROCESSES IN VIBRATIONALLY HIGHLY EXCITED CYCLOHEPTATRIENES .1. THERMAL-ISOMERIZATION IN SHOCK-WAVES

The thermal unimolecular isomerization reactions of cycloheptatriene, and of methyl-, ethyl-, and isopropyl-cycloheptatriene, have been studied over the temperature range 900-1400 K in shock waves. Even for these large molecules, falloff behavior has to be taken into account mainly due to weak collision effects. The limiting high pressure rate constants k∞ and the specific rate constants k (E) are derived for use in later photoactivation experiments. © 1979 American Institute of Physics.