Abstract
In this paper, we focus on the multiple-channel reactions of CH2XO (X = F, Cl, Br) radicals with the NO radical by means of direct dynamic methods. All structures of the stationary points were obtained at the MP2/6-311+G(d,p) level and vibrational frequency analysis was also performed at this level of theory. The minimum energy path (MEP) was obtained via the intrinsic reaction coordinate (IRC) theory at the MP2/6-311+G(d,p) level, and higher-level energetic information was refined by the MC-QCISD method. The rate constants for the three hydrogen abstraction reaction channels over the temperature range 200–1,500 K were calculated by the improved canonical variational transition state theory (ICVT) with a correction for small-curvature tunneling (SCT). The rate constants calculated in this manner were in good agreement with the available experimental data, and the three-parameter rate–temperature formulae for the temperature range 200–1,500 K were \( {k_{1{\text{a}} }}(T)=0.32\times {10^{-18 }}{T^{1.83 }}\exp \left( {1748.54/T} \right) \), \( {k_{2{\text{a}} }}(T)=0.22\times {10^{-19 }}{T^{2.19 }}\exp \left( {1770.19/T} \right) \), \( {k_{3{\text{a}} }}(T)=0.88\times {10^{-20 }}{T^{2.20 }}\exp \left( {1513.82/T} \right) \) (in units of cm3 molecule−1 s−1).
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Acknowledgments
The authors thank Professor Donald G. Truhlar for providing the program POLYRATE 9.7. This work was supported by the National Natural Science Foundation of China (20973077 and 20973049), the Program for New Century Excellent Talents in University (NCET), the Doctor Foundation by the Ministry of Education, the Doctoral Fund of Ministry of Education of China (20112303110005), the Foundation for the Department of Education of Heilongjiang Province (1152G010, 11551077), the Key Subject of Science and Technology program from the Ministry of Education of China, and the SF for Leading Experts in Academe of Harbin of China (2011RFJGS026).
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Li, Y., Zhang, H., Chen, Q. et al. Theoretical study of the reaction of CH2XO (X = F, Cl, Br) radicals with the NO radical. J Mol Model 19, 1391–1397 (2013). https://doi.org/10.1007/s00894-012-1699-2
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DOI: https://doi.org/10.1007/s00894-012-1699-2