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Author(s):   Estupinan, E.; Villenave, E.; Raoult, S.; Rayez, J.C.; Rayez, M.T.; Lesclaux, R.
Title:   Kinetics and mechanism of the gas-phase reaction of the cyclohexadienyl radical c-C6H7 with O2
Journal:   Phys. Chem. Chem. Phys.
Volume:   5
Page(s):   4840 - 4845
Year:   2003
Reference type:   Journal article
Squib:   2003EST/VIL4840-4845

Reaction:   1,4-Cyclohexadiene + ·Cl → 2-chlorocyclohex-4-en-1-yl
Reaction order:   2
Reference reaction:   1,4-Cyclohexadiene + ·Cl → Products
Reference reaction order:   2
Temperature:   302 - 456 K
Rate expression:   6.2x10-1±6.0x10-2
Category:  Experiment
Data type:   Relative rate value measured
Pressure dependence:   None reported
Experimental procedure:   Static or low flow - Data taken vs time
Excitation technique:   Flash photolysis (laser or conventional)
Time resolution:   In real time
Analytical technique:   Vis-UV absorption
Comments:   The authors investigated the kinetics and mechanism of the gas-phase reaction of the cyclohexadienyl radical c-C6H7 with O2 using both experimental and theoretical approaches.Experimentally, cyclohexadienyl radicals were generated by flash photolysis of Cl2 in the presence of 1,4-cyclohexadiene. Cyclohexadienyl radicals were monitored via their time-resolved absorption at 302 nm. The global reaction is believed to consist of two processes:
c-C6H7 + O2 = c-C6H7O2
c-C6H7 + O2 = c-C6H6 + HO2

Theoretical: Energies and optimised geometries were calculated at the DFT-B3LYP/6-31G(d) level oftheory. Single point energy calculations were performed with the coupled cluster CCSD(T)/6-31G(d,p) method, based on the B3LYP/6-31G(d) optimised structures. Zero-point energy corrections were obtained from the calculated DFT-B3LYP frequencies. Thermal energy corrections as well as entropies were obtained from vibrational frequencies and rotational constants.All calculations were performed with the Gaussian98.

The authors derived this rate as part of the experimental procedure to generate cyclohexadienyl but do not provide details.

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