Collision-induced Energy Transfer and Bond Dissociation in Toluene by H2/D2

Energy transfer and bond dissociation of $C-H_{methyl}$ and $C-H_{ring}$ in excited toluene in the collision with $H_2$ and $D_2$ have been studied by use of classical trajectory procedures at 300 K. Energy lost by the vibrationally excited toluene to the ground-state $H_2/D_2$ is not large, but the amount increases with increasing vibrational excitation from 5000 and $40,000cm^{-1}$. The principal energy transfer pathway is vibration to translation (V-T) in both systems. The vibration to vibration (V-V) step is important in toluene + $D_2$, but plays a minor role in toluene + $H_2$. When the incident molecule is also vibrationally excited, toluene loses energy to $D_2$, whereas it gains energy from $H_2$ instead. The overall extent of energy loss is greater in toluene + $D_2$ than that in toluene + $H_2$. The different efficiency of the energy transfer pathways in two collisions is mainly due to the near-resonant condition between $D_2$ and C-H vibrations. Collision-induced dissociation of $C-H_{methyl}$ and $C-H_{ring}$ bonds occurs when highly excited toluene ($55,000-70,400cm^{-1}$) interacts with the ground-state $H_2/D_2$. Dissociation probabilities are low ($10^{-5}{\sim}10^{-2}$) but increase exponentially with rising vibrational excitation. Intramolecular energy flow between the excited C-H bonds occurring on a subpicosecond timescale is responsible for the bond dissociation.