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Reaction of OH radical with mono‐, di‐, and trichloroacetaldehyde: an ab initio study
Author(s) -
Chandra Asit K.,
Uchimaru Tadafumi
Publication year - 2001
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.1104
Subject(s) - hydrogen atom abstraction , chemistry , ab initio , halogen , reactivity (psychology) , radical , computational chemistry , abstraction , hydrogen , ab initio quantum chemistry methods , molecule , organic chemistry , pathology , medicine , philosophy , alkyl , alternative medicine , epistemology
The hydrogen abstraction reactions between chlorine‐substituted acetaldehydes and OH radicals have been investigated by using ab initio molecular orbital theory. Equilibrium geometries and transition‐state structures have been optimized at the (U)MP2/6‐311G(d,p) level. Activation barriers and heats of reaction for different reaction channels have been estimated from the single‐point calculations at the (U)MP2/6‐311G(2df,2p) level. Three, two, and one hydrogen abstraction channel have been found for the mono‐, di‐, and trichloroacetaldehyde, respectively. At a higher temperature region, hydrogen abstraction from the formyl group is found to be the major reaction channel for all the three chloroacetaldehydes. The effect of halogen substitution on reactivity toward hydrogen abstraction has been discussed. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1509–1521, 2001