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CH 3 NHNH 2 + OH reaction: Mechanism and dynamics studies
Author(s) -
Liu HongXia,
Wang Ying,
Yang Lei,
Liu JingYao,
Gao Hong,
Li ZeSheng,
Sun ChiaChung
Publication year - 2009
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.21228
Subject(s) - chemistry , conformational isomerism , hydrogen atom abstraction , reaction rate constant , potential energy surface , radical , hydrogen , transition state theory , computational chemistry , basis set , atmospheric temperature range , ab initio , thermodynamics , molecule , density functional theory , kinetics , physics , quantum mechanics , organic chemistry
A direct dynamics study was carried out for the multichannel reaction of CH 3 NHNH 2 with OH radical. Two stable Conformers (I, II) of CH 3 NHNH 2 are identified by the rotation of the CH 3 group. For each conformer, five hydrogen‐abstraction channels are found. The reaction mechanisms of product radicals (CH 3 NNH 2 and CH 3 NHNH) with OH radical are also investigated theoretically. The electronic structure information on the potential energy surface is obtained at the B3LYP/6‐311G(d,p) level and the energetics along the reaction path is refined by the BMC‐CCSD method. Hydrogen‐bonded complexes are presented at both the reactant and product sides of the five channels, indicating that the reaction may proceed via an indirect mechanism. The influence of the basis set superposition error (BSSE) on the energies of all the complexes is discussed by means of the CBS‐QB3 method. The rate constants of CH 3 NHNH 2 + OH are calculated using canonical variational transition‐state theory with the small‐curvature tunneling correction (CVT/SCT) in the temperature range of 200–1000 K. Slightly negative temperature dependence of rate constant is found in the temperature range from 200 to 345 K. The agreement between the theoretical and experimental results is good. It is shown that for Conformer I, hydrogen‐abstraction from NH position is the primary pathway at low temperature; the hydrogen‐abstraction from NH 2 is a competitive pathway as the temperature increases. A similar case can be concluded for Conformer II. The overall rate constant is evaluated by considering the weight factors of each conformer from the Boltzmann distribution function, and the three‐term Arrhenius expressions are fitted to be k T = 1.6 × 10 −24 T 4.03 exp (1411.5/ T ) cm 3 molecule −1 s −1 between 200–1000 K. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2009