Theoretical Study of Intramolecular H-Migration Reactions of Peroxyl Radicals of JP-10 (Exo-Tetrahydrodicyclopentadiene)

Intramolecular H-migration reactions of peroxyl radicals of JP-10 (C10H15OO center dot) play an important role in developing the oxidation mechanism of JP-10 at low temperature. However, accurate rate coefficients for these reactions are lacking in the literature. Therefore, 33 H-migration reactions of C10H15OO center dot, which belong to six series of reactions, were investigated. Quantum chemical computations at the CBS-QB3 level reveal that C10H15OO center dot do not obey the rule that the energy barrier of 1,4-H migration reaction is higher than that of 1,5-H migration reaction because of the special steric cyclic structure of C10H15OO center dot and the ring strain in the transition state. The transition state theory and Rice-Ramsberger-Kassel-Marcus/Master-Equation theory were used to obtain high-pressure limit rate coefficients and pressure-dependent rate coefficients, respectively. The results show that H-migration reactions of C10H15OO center dot have obvious pressure-dependent effect. The most competitive reaction was obtained among 33 reactions. Moreover, branching ratios of each series of reactions were used as weight ratios to lump this series of reactions. Six series of reactions were lumped as six lumped reactions by the isomer lumping method. This will provide accurate rate coefficients for constructing a mechanism with the low number of species and suitability for computational fluid dynamics simulation.