Theoretical study of the pyrolysis of methyltrichlorosilane in the gas phase. 3. Reaction rate constant calculations.

Yingbin Ge, Mark S Gordon, Francine Battaglia, Rodney O Fox

文献索引：J. Phys. Chem. A 114(6) , 2384-92, (2010)

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摘要

The rate constants for the gas-phase reactions in the silicon carbide chemical vapor deposition of methyltrichlorosilane (Ge, Y. B.; Gordon, M. S.; Battaglia, F.; Fox, R. O. J. Phys. Chem. A 2007, 111, 1462.) were calculated. Transition state theory was applied to the reactions with a well-defined transition state; canonical variational transition state theory was applied to the barrierless reactions by finding the generalized transition state with the maximum Gibbs free energy along the reaction path. Geometry optimizations were carried out with second-order perturbation theory (MP2) and the cc-pVDZ basis set. The partition functions were calculated within the harmonic oscillator and rigid rotor approximations. The final potential energy surfaces were obtained using the left-eigenstate coupled-cluster theory, CR-CC(2,3) with the cc-pVTZ basis set. The high-pressure approximation was applied to the unimolecular reactions. The predicted rate constants for more than 50 reactions were compared with the experimental ones at various temperatures and pressures; the deviations are generally less than 1 order of magnitude. Theory is found to be in reasonable agreement with the experiments.