| Abstract
| - Stationary points of paths for H atom abstraction from CH3NHNH2 (monomethylhydrazine) by NO2 werecharacterized via CCSD(T)/6-311++G(3df,2p)//MPWB1K/6-31+G(d,p) and CCSD(T)/6-311+G(2df,p)//CCSD/6-31+G(d,p) calculations. Five transition states connecting CH3NHNH2−NO2 complexes to a manifoldthat includes CH3NHNH−HONO, CH3NNH2−HONO, CH3NNH2−HNO2, and CH3NHNH−HNO2 complexeswere identified. Transition states that connect CH3NHNH−HONO, CH3NNH2−HONO, CH3NNH2−HNO2,and CH3NHNH−HNO2 complexes to each other via H atom exchange and/or hindered internal rotation werealso identified. The high point in the minimum energy path from the CH3NHNH2 + NO2 reactant asymptoteto the manifold of HONO-containing product states is a transition state 8.6 kcal/mol above the reactantasymptote. From a kinetics standpoint, this value is considerably higher than the 5.9 kcal/mol value that wasestimated for it based on theoretical results for H atom abstraction from NH3 by NO2.
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