Effect of reagent vibrational excitation on the dynamics of the Cl + HD → HCl(DCl) + D(H) reaction

The effect of vibrational excitation of the HD reagent on the reaction dynamics of the Cl + HD(v = 0, 1, j = 0) → HCl(DCl) + D(H) system has been investigated by means of quasi-classical trajectory calculations on a new ab initio potential energy surface (PES) at several collision energies. It has been observed that, whereas the scattering is backward in both channels when the reaction is carried out from HD(v = 0), it becomes predominantly forward if the reaction takes place with HD in v = 1. The results are compared with recent experimental data for the photo-nitiated Cl + CH4(ν3 = 1) → HCl + CH3 reaction and discussed in terms of the role of the impact parameter on the dynamics and the orientation of the reagents on a strongly collinear PES.