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Computational Study of the Rate Coefficients for the Reactions of NO2 with CH3NHNH, CH3NNH2, and CH2NHNH2

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journal contribution
posted on 16.07.2015, 00:00 by Nozomu Kanno, Hiroumi Tani, Yu Daimon, Hiroshi Terashima, Norihiko Yoshikawa, Mitsuo Koshi
The reactions of NO2 with cis-/trans-CH3NHNH, CH3NNH2 and CH2NHNH2 have been studied theoretically by quantum chemical calculations and steady-state unimolecular master equation analysis based on RRKM theory. The barrier heights for the roaming transition states between nitro (RNO2) and nitrite (RONO) isomerization reactions and those for the concerted HONO and HNO2 elimination reactions from RNO2 and RONO, affect the pressure dependences of the product-specific rate coefficients. At ambient temperature and pressure, the dominant product of the reactions of NO2 with cis-/trans-CH3NHNH and CH2NHNH2 would be expected to be HONO with trans-CH3NNH and CH2NNH2, respectively, whereas it is CH3N­(NH2)­NO2 for CH3NNH2 + NO2. The product-specific rate coefficients for the titled and related reactions on the same potential energy surfaces were proposed for kinetics modeling.