Isotope Effects on the Energy Flow and Bond Dissociations of Excited α-Chlorotoluene in Collisions with H2/D2

摘要

We have studied the vibrational relaxation of excited α-chlorotoluene and dissociations of C-H_(ring) and C-Cl bonds of oc-chlorotoluene in the oc-chlorotoluene + H2/D2 collision at 300 K using classical trajectory procedure.The vibrational energy loss of excited oc-chlorotoluene by the collision of the ground-state H2/D2 is small,but it increases with increasing the total vibrational excitation,E_T-The magnitude of energy loss was significantly larger in the oc-CT + D2 system,especially for values of E_T above 30 000 cm~(-1).Moreover,the vibrational relaxation of α-CT was found to be primarily because of the C-Cl vibrational decay.Furthermore,the D2 molecule induced stronger perturbations on the oc-CT molecule,which enhanced the vibrational relaxation of oc-CT.Dissociation probabilities in both systems,which were initially low,rapidly increased with an increase in the total vibrational excitation.The C-Cl bond dissociation probability was found to be lower than that of C-H_(ring) at values of E_T slightly below 70 000 cm~(-1),because the probability of the C-Cl bond gaining sufficient energy for dissociation was low compared to that of the C-H_(ring) bond.The dissociation probabilities of the C-H_(ring) and C-Cl bonds in the oc-CT + D2 collision system were found to be higher than those in the oc-CT + H2 system,because of more efficient perturbation in the former.