Kinetics Database Resources
Title: C-C bond fission pathways of chloroalkenyl alkoxy radicals
Journal: J. Chem. Phys.
Page(s): 1794 - 1801
Reference type: Journal article
CH2=CHC(CH3)(O·)CH2Cl → CH2=CHCOCH3 + ·CH2Cl
The authors caried out density-functional theory and ab initio molecular orbital calculations todetermine the structures and energetics of the chloroalkenyl alkoxy radicals arising from Cl-initiatedreactions of isoprene. The transition states and products of their decomposition reactions were determined and transition state theory was used to calculate high-pressure limit decomposition rates.
Geometry optimizations of the various species were performed at the Becke three parameter Lee?Yang?arr ~B3LYP!/6-31G(d,p) level, and single-point energies were computed usingsecond-order M?er?lesset and coupled-cluster theory with single and double excitationsincluding perturbative corrections for the triple excitations.
The results indicate that C? bond decomposition of the chloroalkenyl alkoxy radicals is relatively slow and likely plays a minor role in the Cl-isoprene reactions. The authors discuss the Implications of their results on the formation yields of methyl vinyl ketone, methacrolein, and 1-chloro-3-methyl-3-buten-2-one.
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