Unimolecular isomerization/decomposition of cyclopentadienyl and related bimolecular reverse process: ab initio MO/statistical theory study

The cyclopentadienyl radical decomposition has been studied in detail by high-level correlation MO methods combined with multichannel RRKM rate constant calculations. The product channels of the reaction were examined by calculating their pressure-dependent branching rate constants. The overall reaction rate has been shown to be controlled by the first transition state corresponding to 1,2-hydrogen atom migration. Also, the reverse bimolecular reactions (C3H3 + C2H2→ products) have been included in the study. We provide a summary of pressure dependent rate constant expressions for the 1000–3000 K temperature range that may be useful for kinetic modeling of relevant combustion systems. c © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 415–425, 2000