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Isotope Effects on the Energy Flow and Bond Dissociations of Excited α‐Chlorotoluene in Collisions with H 2 / D 2
Author(s) -
Lee Sang Kwon,
Ree Jongbaik
Publication year - 2021
Publication title -
bulletin of the korean chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.237
H-Index - 59
ISSN - 1229-5949
DOI - 10.1002/bkcs.12258
Subject(s) - excited state , chemistry , dissociation (chemistry) , vibrational energy relaxation , excitation , bond dissociation energy , atomic physics , molecule , relaxation (psychology) , ground state , physics , psychology , social psychology , organic chemistry , quantum mechanics
We have studied the vibrational relaxation of excited α‐chlorotoluene and dissociations of CH ring and CCl bonds of α‐chlorotoluene in the α‐chlorotoluene + H 2 /D 2 collision at 300 K using classical trajectory procedure. The vibrational energy loss of excited α‐chlorotoluene by the collision of the ground‐state H 2 /D 2 is small, but it increases with increasing the total vibrational excitation, E T . The magnitude of energy loss was significantly larger in the α‐CT + D 2 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 CCl vibrational decay. Furthermore, the D 2 molecule induced stronger perturbations on the α‐CT molecule, which enhanced the vibrational relaxation of α‐CT. Dissociation probabilities in both systems, which were initially low, rapidly increased with an increase in the total vibrational excitation. The CCl bond dissociation probability was found to be lower than that of CH ring at values of E T slightly below 70 000 cm −1 , because the probability of the CCl bond gaining sufficient energy for dissociation was low compared to that of the CH ring bond. The dissociation probabilities of the CH ring and CCl bonds in the α‐CT + D 2 collision system were found to be higher than those in the α‐CT + H 2 system, because of more efficient perturbation in the former.