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Chemical effects of radical vibrational energy content on the abstraction reaction: CF 3 + Br 2 → CF 3 Br + Br
Author(s) -
Young Mark A.,
Pimentel George C.
Publication year - 1991
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550230107
Subject(s) - chemistry , bromine , radical , photodissociation , chemical reaction , molecule , activation energy , photochemistry , molecular vibration , vibrational energy , computational chemistry , organic chemistry
We have studied the effect of vibrational mode activation in the CF 3 radical on the bromine abstraction reaction; CF 3 + Br 2 → CF 3 Br + Br. Excess vibrational energy resides in the symmetric modes of the radical after 248 nm photolysis of the parent molecule, CF 3 I. Our data indicate that the hot radicals react no faster than thermalized CF 3 , and may actually have a lower cross‐section for reaction. Dynamical factors that result in poor coupling of the vibrational energy to the reaction coordinate, as well as other similar considerations, could be responsible for the experimental observations. In addition, we have made an independent determination of the rate for the bromine abstraction reaction of (1.08 ± .13) × 10 12 s −1 cm 3 mol −1 .