Unimolecular processes in vibrationally highly excited cycloheptatrienes. I. 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.