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

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• 作者：Nozomu Kanno ; Hiroumi Tani ; Yu Daimon ; Hiroshi Terashima ; Norihiko Yoshikawa ; Mitsuo Koshi
• 刊名：Journal of Physical Chemistry A
• 出版年：2015
• 出版时间：July 16, 2015
• 年：2015
• 卷：119
• 期：28
• 页码：7659-7667
• 全文大小：480K
• ISSN：1520-5215

文摘

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.