Ab initio quantum chemical studies of the reactions of CF3CFHO2 with HO2 |
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| Authors: | Weichao Zhang Benni Du |
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| Institution: | 1. Department of Chemistry, Xuzhou Normal University, Xuzhou, Jiangsu 221116, People's Republic of ChinaDepartment of Chemistry, Xuzhou Normal University, Xuzhou, Jiangsu 221116, People's Republic of China;2. Department of Chemistry, Xuzhou Normal University, Xuzhou, Jiangsu 221116, People's Republic of China |
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| Abstract: | The potential energy surface (PES) for the CF3CFHO2+HO2 reaction has been theoretically investigated using the DFT B3LYP/6‐311G(d,p)] and B3LYP/6‐311++G(3df,3pd)//B3LYP/6‐311G(d,p) levels of theory. Both singlet and triplet PESs are investigated. The reaction mechanism on the triplet surface is simple. It is revealed that the formation of CF3CFHOOH+3O2 is the dominant channel on the triplet surface. On the basis of the ab initio data, the total rate constants for the reaction CF3CFHO2+HO2 in the T = 210–500 K range have been computed using conventional transition state theory with Wigner's tunneling correction and have been fitted by a rate constant expression as k = 1.04 ×10?12(cm3 molecule?1 s?1) exp (700.33/T). Calculated transition state rate constants with Wigner's tunneling correction for the reaction CF3CFHO2+HO2 are in good agreement with the available experimental values. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 |
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| Keywords: | DFT theory TST rate constant CF3CFHO2 HO2 |
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