Unimolecular processes in vibrationally highly excited cycloheptatrienes. I. Thermal isomerization in shock waves

摘要

The thermal unimolecular isomerization reactions of cycloheptatriene, and of methylhyphen; , ethylhyphen; , and isopropylhyphen;cycloheptatriene, have been studied over the temperature range 900ndash;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 constantskinfin;and the specific rate constantsk(E) are derived for use in later photoactivation experiments.