Ab initio kinetics on cyclohexylperoxy radical: The product of oxygen addition to cyclohexyl

The chemistry of cyclohexylperoxy radical was investigated using ab initio theoretical approach. The geometries and frequencies of all stationary points on the potential energy surfaces were evaluated at B3LYP/6-311+ +G(d,p) level and the energies were refined at DLPNO-CCSD(T)/CBS level. Then the rate constants of all reactions were computed based on TST theory and the pressure-dependent effects were evaluated using RRKM/ME theory. The present rate constants were proved to reduce ignition delay times of cyclohexane at NTC region and to enhance dissociation rate of cyclohexane at 550-750 K, in comparison with results obtained with a previous cyclohexane low-temperature mechanism.