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Radical reaction HCNO + 3NH: a mechanistic study

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Abstract

The complex triplet potential energy surface for the reaction of HCNO with NH is investigated at the G3B3 level using the B3LYP/6-311++G(d,p), and QCISD/6-311++G(d,p) geometries. Various possible isomerization and dissociation pathways are probed. The initial association between HCNO and NH is found to be carbon to nitrogen attack leading to HNCHNO 2a, which can convert to 2b, 2c, and 2d. Subsequently, 1,4-H-shift of 2a to form NCHNOH 3a followed by dissociation to P 2 (1HCN + 3HON) is the most feasible pathway. Much less competitively, 2d undergoes successive 1,3-H-shift and C-N cleavage to form HNCNOH 8b, and then to product P 3 (1HNC + 3HON), the second feasible pathway. 8b can alternatively isomerize to 8c followed by N–O bond rupture to generate P 6 (2OH + 2HNCN), the lesser followed feasible pathway. In addition, 2b takes continuously 1,3- and 1,2-H-shift to form NC(H)NHO 6a, then to ONHCNH 7a which can convert to 7b. Eventually, 7b may take C-N bond fission to produce P 5 (1HNC + 3HNO), the least feasible pathway. The present paper may be helpful for future experimental identification of the product distributions for the title reaction, and may be helpful to deeply understand the mechanism of the title reaction.

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Acknowledgments

This work is supported by the National Natural Science Foundation of China (Nos. 20773048).

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Authors and Affiliations

  1. State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, 130023, Changchun, People’s Republic of China

    Yan Li, Hui-ling Liu, Yan-bo Sun, Zhuo Li, Xu-ri Huang & Chia-chung Sun

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  1. Yan Li
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  2. Hui-ling Liu
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  3. Yan-bo Sun
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Correspondence to Xu-ri Huang.

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Li, Y., Liu, Hl., Sun, Yb. et al. Radical reaction HCNO + 3NH: a mechanistic study. Theor Chem Acc 124, 123–137 (2009). https://doi.org/10.1007/s00214-009-0591-3

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