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| - Kinetics of the Reaction of Methyl Radical with Hydroxyl Radical and MethanolDecomposition
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| - The CH3 + OH bimolecular reaction and the dissociation of methanol are studied theoretically at conditionsrelevant to combustion chemistry. Kinetics for the CH3 + OH barrierless association reaction and for the H+ CH2OH and H + CH3O product channels are determined in the high-pressure limit using variable reactioncoordinate transition state theory and multireference electronic structure calculations to evaluate the fragmentinteraction energies. The CH3 + OH → 3CH2 + H2O abstraction reaction and the H2 + HCOH and H2 +H2CO product channels feature localized dynamical bottlenecks and are treated using variational transitionstate theory and QCISD(T) energies extrapolated to the complete basis set limit. The 1CH2 + H2O productchannel has two dynamical regimes, featuring both an inner saddle point and an outer barrierless region, andit is shown that a microcanonical two-state model is necessary to properly describe the association rate forthis reaction over a broad temperature range. Experimental channel energies for the methanol system arereevaluated using the Active Thermochemical Tables (ATcT) approach. Pressure dependent, phenomenologicalrate coefficients for the CH3 + OH bimolecular reaction and for methanol decomposition are determined viamaster equation simulations. The predicted results agree well with experimental results, including those froma companion high-temperature shock tube determination for the decomposition of methanol.
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