Energy Transfer and Bond Dissociation in the o‐chlorotoluene + H2/Cl2/HCl Collisions

Abstract

Energy flow and C–H and C–Cl bond dissociations in o‐chlorotoluene (OCT) in collisions with H2, Cl2, and HCl are studied using classical trajectory methods. The energy loss by the excited OCT is small, but it increases with increasing total vibrational energy content ET of OCT between 5000 cm−1 and 30000 cm−1. The energy loss is larger in OCT + HCl collision than in OCT + H2 or OCT + Cl2. The difference is mainly due the near‐resonant conditions between the vibration of the incident molecule and the C–H or C–Cl vibrations. Intermolecular energy transfer occurs through vibration–translation (V–T) and vibration–vibration (V–V) pathways. The intramolecular energy flow between C–H and C–Cl in highly excited OCT (60000–60300 cm−1) leads to bond dissociation. The probabilities of C–H and C–Cl dissociation are 10−5–10−1 and increase exponentially with increasing vibrational excitation of OCT. The probabilities are found to increase when the incident molecule becomes heavier.