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Kinetics and mechanism for the H‐for‐X exchange process in the H + C 6 H 5 X reactions: A computational study
Author(s) -
Tokmakov I. V.,
Lin M. C.
Publication year - 2001
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.1062
Subject(s) - isodesmic reaction , chemistry , reaction rate constant , toluene , benzene , radical , ab initio , density functional theory , computational chemistry , elementary reaction , disproportionation , kinetics , kinetic energy , thermodynamics , organic chemistry , catalysis , physics , quantum mechanics
Abstract The addition of H atoms to benzene and toluene and subsequent transformations were investigated using high level ab initio and density functional theory methods. Molecular structures and vibrational frequencies calculated at the B3LYP/6‐311++G(d,p) level of theory were used in combination with adjusted G2M energetic parameters for RRKM rate constant calculations. Standard heats of formation for cyclohexadienyl and cyclohexadienyl, 6‐methyl radicals calculated through isodesmic reactions amounted to 49.5 ± 2 and 42.9 ± 3 kcal/mol, respectively. Rate constants for various elementary reactions involved in the H‐for‐X exchange (X = D, CH 3 ) were calculated and closely correlated with the available experimental kinetic data. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 633–653, 2001