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Direct ab initio study on the rate constants of radical C2(A3Πu) + C3H8 reaction

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Abstract

The mechanism and kinetics of the radical 3C2 + C3H8 reaction have been investigated theoretically by direct ab initio kinetics over a wide temperature range. The potential energy surfaces have been constructed at the CCSD(T)/B3//UMP2/B1 levels of theory. The electron transfer was also analyzed by quasi–restricted orbital (QRO) in detail. It was shown that all these channels proceed exclusively via hydrogen abstraction. The overall ICVT/SCT rate constants are in agreement with the available experimental results. The prediction shows that the secondary hydrogen of C3H8 abstraction by 3C2 radical is the major pathway at low temperatures (below 700 K), while as the temperature increases, the primary hydrogen of C3H8 abstraction becomes more important and more favorable. A negative temperature dependence of the rate constants for the reaction of 3C2 + C3H8 was observed. The three–(k 3) and four–parameter (k 4) rate-temperature expressions were also provided within 243–2000 K to facilitate future experimental studies.

Three types of hydrogen abstraction from C3H8 by 3C2 radical have been considered. The prediction shows that the secondary hydrogen of C3H8 abstraction by 3C2 radical is the major pathway.

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Acknowledgments

This work is supported by the National Natural Science Foundation of China (NSFC No. 21073075), Research Fund for the Doctoral Program of Higher Education of China (RFDP No. 20100061110046), the Special Funding of State Key Laboratory of Theoretical and Computational Chemistry, Jilin University and Basic Research Fund of Jilin University (No. 421010061439, 450060445067) and Graduate Innovation Fund of Jilin University (No.20121036). The authors are thankful for the reviewers’ invaluable comments.

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Authors and Affiliations

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

    Rui-Ping Huo, Xu-Ri Huang, Ji-Lai Li & Chia-Chung Sun

  2. School of Chemistry and Materials Science, Shanxi Normal University, Linfen, 041004, People’s Republic of China

    Xiang Zhang

  3. Department of Theoretical Chemistry, Lund University, Chemical Centre, P.O. Box 124, SE-221 00, Lund, Sweden

    Ji-Lai Li

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  1. Rui-Ping Huo
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  2. Xiang Zhang
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Correspondence to Ji-Lai Li.

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Huo, RP., Zhang, X., Huang, XR. et al. Direct ab initio study on the rate constants of radical C2(A3Πu) + C3H8 reaction. J Mol Model 19, 1009–1018 (2013). https://doi.org/10.1007/s00894-012-1616-8

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  • DOI: https://doi.org/10.1007/s00894-012-1616-8

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