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Journal of Physical Chemistry A, Vol.109, No.31, 6791-6795, 2005
How active is the bend excitation of methane in the reaction with O(P-3)?
The role of bending excitation of methane in the reaction with O(P-3) is investigated in a crossed-beam experiment. Previous theories predicted that either stretch or bend excitation of the reactant promotes chemical reactivity and that initial bending excitation of CH4 preferentially yields umbrella-excited CH3 products. Experimentally, both predictions for bend-excited reagent were not borne out in this investigation. We found instead that compared to the ground-state reagent, bend-excited methane yields more vibrational excitation of the hydroxyl coproduct. The first reported product angular distributions show predominant backward scatterings for both ground-state and bend-excited methanes, which corroborate well with a direct rebound reaction mechanism.