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Ab initio study on the structures of fluorinated formates and hydrogen abstraction reaction with OH radical
Author(s) -
Chandra Asit K.,
Uchimaru Tadafumi,
Sugie Masaaki,
Sekiya Akira
Publication year - 2003
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.10180
Subject(s) - hydrogen atom abstraction , chemistry , formate , conformational isomerism , radical , ab initio , computational chemistry , transition state theory , hydrogen , reaction rate constant , fluorine , methyl formate , ab initio quantum chemistry methods , abstraction , photochemistry , molecule , methanol , organic chemistry , catalysis , kinetics , physics , quantum mechanics , philosophy , epistemology
Abstract The conformational potential energy surfaces for mono‐ and difluoromethyl formate have been determined by using a modified G2(MP2) level of calculations. The structures and vibrational frequencies for the conformers of mono‐ and difluoromethyl formate have been reported. The hydrogen abstraction reaction channels between these two formates and OH radicals have been studied at the same level of theory. Using the standard transition state theory and taking into account the effect of tunneling across the reaction barrier, we have estimated the rate constant for hydrogen abstraction by OH radical. The effect of successive fluorine substitution for methyl hydrogen on the conformational stability and on the hydrogen abstraction rate has been analyzed. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 396–407, 2003