Gas-phase kinetics study of reaction of OH radical with CH 3NHNH 2 by second-order multireference perturbation theory

Hongyan Sun, Peng Zhang, Chung K. Law

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Abstract

The gas-phase kinetics of H-abstraction reactions of monomethylhydrazine (MMH) by OH radical was investigated by second-order multireference perturbation theory and two-transition-state kinetic model. It was found that the abstractions of the central and terminal amine H atoms by the OH radical proceed through the formation of two hydrogen bonded preactivated complexes with energies of 6.16 and 5.90 kcal mol -1 lower than that of the reactants, whereas the abstraction of methyl H atom is direct. Due to the multireference characters of the transition states, the geometries and ro-vibrational frequencies of the reactant, transition states, reactant complexes, and product complexes were optimized by the multireference CASPT2/aug-cc-pVTZ method, and the energies of the stationary points of the potential energy surface were refined at the QCISD(T)/CBS level via extrapolation of the QCISD(T)/cc-pVTZ and QCISD(T)/cc-pVQZ energies. It was found that the abstraction reactions of the central and two terminal amine H atoms of MMH have the submerged energy barriers with energies of 2.95, 2.12, and 1.24 kcal mol -1 lower than that that of the reactants respectively, and the abstraction of methyl H atom has a real energy barrier of 3.09 kcal mol -1. Furthermore, four MMH radical-H 2O complexes were found to connect with product channels and the corresponding transition states. Consequently, the rate coefficients of MMH + OH for the H-abstraction of the amine H atoms were determined on the basis of a two-transition-state model, with the total energy E and angular momentum J conserved between the two transition-state regions. In units of cm 3 molecule -1 s -1, the rate coefficient was found to be k 1 = 3.37 × 10 -16T 1.295 exp(1126.17/T) for the abstraction of the central amine H to form the CH 3N NH 2 radical, k 2 = 2.34 × 10 -17T 1.907 exp(1052.26/T) for the abstraction of the terminal amine H to form the trans-CH 3NHN H radical, k 3 = 7.41 × 10 -20T 2.428 exp(1343.20/T) for the abstraction of the terminal amine H to form the cis-CH 3NHN H radical, and k 4 = 9.13 × 10 -21T 2.964 exp(-114.09/T) for the abstraction of the methyl H atom to form the C H 2NHNH 2 radical, respectively. Assuming that the rate coefficients are additive, the total rate coefficient of these theoretical predictions quantitatively agrees with the measured rate constant at temperatures of 200-650 K, with no adjustable parameters.

Original languageEnglish (US)
Pages (from-to)5045-5056
Number of pages12
JournalJournal of Physical Chemistry A
Volume116
Issue number21
DOIs
StatePublished - May 31 2012

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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