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Theoretical mechanistic study on the reaction of the methoxymethyl radical with nitrogen dioxide

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Abstract

Mechanism of the reaction of CH3OCH2 with NO2 is explored theoretically at the M062X/MG3S and G4 levels. The calculated results indicate two stable association intermediates, CH3OCH2NO2 (IM1) and CH3OCH2ONO (IM2), which can be produced by the attack of the nitrogen or oxygen atom of NO2 to terminal carbon atom of CH3OCH2 without barrier involved. IM2 is found to take trans (IM2a)–cis (IM2b) conversion and isomerization to IM1, with the following stability order IM2a > IM2b > IM1. Starting from IM2a, the most feasible pathway is the direct O−NO bond cleavage leading to P1 (CH3OCH2O + NO) or the H-shift and O−NO bond rupture to produce P2 (CH3OCHO + HNO), both of which have comparable contribution to the title reaction. There also involves an H-transfer from the methyl group of IM2a to the N atom with the simultaneous dissociations of the C–O and O–N bonds to produce P4 (2CH2O + HNO). In addition, another dissociation pathway is open to IM2b which decompose to P5 (CH2O + CH3ONO) by the O−N and C−O bond scissions and the recombination of CH3O and NO. Because all the intermediates and transition states involved in the above pathways lie below reactants, the CH3OCH2 + NO2 reaction is expected to be rapid. Subsequent dissociation of IM1 and direct H-abstraction between CH3OCH2 and NO2 are kinetically almost inhibited due to significantly high barriers. The present results can lead us to deeply understand the mechanism of the title reaction and may be helpful for understanding NO2 combustion chemistry.

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Funding

This study was funded by the National Natural Science Foundation of China under Grant no. 21606178.

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Authors and Affiliations

  1. School of Chemical Engineering, Northwest University, Xi’an, 710069, China

    Yulei Guan, Xiangrui Meng, Xia Wang, Ru Liu, Haixia Ma & Jirong Song

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  1. Yulei Guan
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  2. Xiangrui Meng
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  3. Xia Wang
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  4. Ru Liu
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  5. Haixia Ma
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  6. Jirong Song
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Contributions

All authors contributed to the study conception and design. Theoretical calculations, data collection, and analysis were performed by Yulei Guan, Xiangrui Meng, Xia Wang, and Liu Ru. The first draft of the manuscript was written by Yulei Guan and Haixia Ma. Review and editing were performed by Jirong Song. All authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

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Correspondence to Yulei Guan.

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Guan, Y., Meng, X., Wang, X. et al. Theoretical mechanistic study on the reaction of the methoxymethyl radical with nitrogen dioxide. J Mol Model 27, 18 (2021). https://doi.org/10.1007/s00894-020-04657-1

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  • DOI: https://doi.org/10.1007/s00894-020-04657-1

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