Abstract
We report a study of the reaction dynamics of the H + CDCl3 → HD(v‘,j‘) + CCl3 reaction with the CDCl3 reactant prepared in the ν1 C−D stretch v‘‘=1 excited state. Stimulated Raman excitation is used to prepare the CDCl3(v‘‘=1) reactant and coherent anti-Stokes Raman scattering is used to detect the HD(v‘,j‘) product, under effectively single-collision conditions at a relative energy of 1.6 eV. Even though the vibrational excitation energy of the reactant (0.28 eV) is small compared to the collision energy, which greatly exceeds the reaction barrier height, the vibrational excitation of the reactant increases the reaction cross section by a factor of 1.66 ± 0.15. Despite this, none of the energy added by the reactant vibrational excitation appears as HD product vibration or rotation. All of it goes into product translation and/or CCl3 internal energy.
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