Theoretical study of the reaction of ethynyl radical with acetonitrile |
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Authors: | Jing-Yu Sun Yi-Zhen Tang Hao Sun Xiu-Juan Jia Xiu-Mei Pan Ya-Ru Pan Rong-Shun Wang |
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Institution: | 1. Faculty of Chemistry, Institute of Functional Material Chemistry, Northeast Normal University, Renmin Road 5268, Changchun, Jilin, 130024, People’s Republic of China
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Abstract: | A detailed computational study has been performed on the mechanism and kinetics of the C2H + CH3CN reaction. The geometries were optimized at the BHandHLYP/6–311G(d, p) level. The single-point energies were calculated using the BMC-CCSD, MC-QCISD and QCISD(T)/6–311+G(2df, 2pd) methods. Five mechanisms were investigated, namely, direct hydrogen abstraction, C-addition/elimination, N-addition/elimination, C2H–to–CN substitution and H-migration. The kinetics of the title reaction were studied using TST and multichannel RRKM methodologies over a wide range of temperatures (150–3,000 K) and pressures (10?4–104 torr). The total rate constants show positive temperature dependence and pressure independence. At lower temperatures, the C-addition step is the most feasible channel to produce CH3 and HCCCN. At higher temperatures, the direct hydrogen abstraction path is the dominant channel leading to C2H2 and CH2CN. The calculated overall rate constants are in good agreement with the experimental data. |
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