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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 34, Number 12
BKCSDE 34(12)
December 20, 2013 

Collision-induced Energy Transfer and Bond Dissociation in Toluene by H2/D2
Jongbaik Ree*, Yoo Hang Kim, Hyung Kyu Shin
Collision-induced, Dissociation, Intramolecular energy flow
Energy transfer and bond dissociation of C-Hmethyl and C-Hring in excited toluene in the collision with H2 and D2 have been studied by use of classical trajectory procedures at 300 K. Energy lost by the vibrationally excited toluene to the ground-state H2/D2 is not large, but the amount increases with increasing vibrational excitation from 5000 and 40,000 cm−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 + D2, but plays a minor role in toluene + H2. When the incident molecule is also vibrationally excited, toluene loses energy to D2, whereas it gains energy from H2 instead. The overall extent of energy loss is greater in toluene + D2 than that in toluene + H2. The different efficiency of the energy transfer pathways in two collisions is mainly due to the near-resonant condition between D2 and C-H vibrations. Collision-induced dissociation of C-Hmethyl and C-Hring bonds occurs when highly excited toluene (55,000-70,400 cm−1) interacts with the ground-state H2/D2. Dissociation probabilities are low (10−5~10−2) 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.
3641 - 3648
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