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Author(s):   Zhang, D.; Zhang, R.
Title:   Unimolecular Decomposition of Nitrooxyalkyl Radicals from NO3-Isoprene Reaction
Journal:   J. Chem. Phys.
Volume:   116
Page(s):   9721 - 9728
Year:   2002
Reference type:   Journal article
Squib:   2002ZHA/ZHA9721-9728

Reaction:   NO3 - isoprene radical adduct → Oxirane + NO2
Reaction order:   1
Temperature:   300 K
Pressure:  1.01 bar
Rate expression:   3.83x10-2 [s-1]
Category:  Theory
Data type:   Transition state theory
Comments:   Theoretical treatment, basis set correction factor based on MP2/6-31G(d)//B3LYP/6-31G(d,p) and MP2/6-311++G(d,p)//B3LYP/6-31G(d,p) and used in CCSD(T)/6-31G(d)//B3LYP/6-31G(d,p)+CF, C5H8O* can either be 2-methyl-2-vinyl-oxirane or 2-(1-methyl-vinyl)oxirane, predict prompt and thermal decomposition of the nitrooxyalkyl radicals using a statistical-dynamical master equation and transition state theory, respectively. There are four initial isomers of the NO3 adduct, the rate coefficients refer to that isomer which is calculated to be the major product (>85%), under atmospheric conditions (300 K, 1 atm pressure) stabilization of the adduct should dominate (97%) with some small formation of the oxirane.

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