State-to-State Dynamics of the H + CDCl₃(v₁‘‘=1) → HD(v‘,j‘) + CCl₃ Reaction

We report a study of the reaction dynamics of the H + CDCl 3 → HD( v ‘, j ‘) + CCl 3 reaction with the CDCl 3 reactant prepared in the ν 1 C−D stretch v ‘‘=1 excited state. Stimulated Raman excitation is used to prepare the CDCl 3 ( 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 CCl 3 internal energy.