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Chemical Sciences Division
Estupinan, E.; Villenave, E.; Raoult, S.; Rayez, J.C.; Rayez, M.T.; Lesclaux, R.|
Kinetics and mechanism of the gas-phase reaction of the cyclohexadienyl radical c-C6H7 with O2
Phys. Chem. Chem. Phys.
4840 - 4845
1,4-Cyclohexadiene + ·Cl → 2-chlorocyclohex-4-en-1-yl
1,4-Cyclohexadiene + ·Cl → Products
Reference reaction order:
302 - 456
Relative rate value measured
Static or low flow - Data taken vs time
Flash photolysis (laser or conventional)
In real time
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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