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Author(s):   Zhang, D.; Zhang, R.Y.; Allen, D.T.
Title:   C-C bond fission pathways of chloroalkenyl alkoxy radicals
Journal:   J. Chem. Phys.
Volume:   118
Page(s):   1794 - 1801
Year:   2003
Reference type:   Journal article
Squib:   2003ZHA/ZHA1794-1801

Reaction:   Methacrolein + ·CH2Cl → CH2=C(CH3)CH(O·)CH2Cl
Reaction order:   2
Temperature:   300 K
Rate expression:   3.9x10-23 [cm3/molecule s]
Category:  Theory
Data type:   Transition state theory
Pressure dependence:   Rate constant is high pressure limit
Comments:   The authors calculate the reaction to be 3.7 kcal/mol exothermic but it is not clear if this number pertains to 0 K or 300 K.

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.


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