Theoretical Study on the Mechanism and Dynamic of CF3CH2CH3 Reaction with OH Radicals

Chem. J. Chinese Universities ›› 2010, Vol. 31 ›› Issue (6): 1240.

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Theoretical Study on the Mechanism and Dynamic of CF₃CH₂CH₃ Reaction with OH Radicals

WANG Yong-Xia, GAO Hong, WANG Qin, LIU Jing-Yao*

State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China

Received:2009-10-10 Online:2010-06-10 Published:2010-06-10
Contact: LIU Jing-Yao. E-mail: ljy121@jlu.edu.cn
Supported by:
国家自然科学基金(批准号: 20333050, 20303007, 20973077)和教育部新世纪优秀人才支持计划(NCET)资助.

Abstract

Abstract:

The optimized geometries and frequencies of all the stationary points involved in each reaction channel of the CF₃CH₂CH₃+OH reaction were calculated at the BB1K/6-31+G(d,p) level, and the potential energy profile is further refined by single-point energy calculations at the BMC-CCSD, MC-QCISD and G3(MP2) levels. The rate constants of all channels were evaluated by variational transition state theory(VTST) at the BMC-CCSD//BB1K, MC-QCISD//BB1K, G3(MP2)//BB1K and BB1K levels over a wide temperature range of 200—1000 K, and the contribution of H-abstraction from the —CH₂ and —CH₃ groups to the total reaction was discussed. The present calculations show that the rate constants evaluated at the BMC-CCSD//BB1K level are in excellent agreement with the available experimental values in the measured tempe-rature range. Finally, the three-parameter rate-temperature expression of the total reaction over the whole temperature range 200—1000 K was given as k=1.90×10^-21T^3.21exp(-292.62/T).

Key words: Direct dynamics; Rate constant; Variational transition-state theory; CF3CH2CH3

TrendMD:

WANG Yong-Xia, GAO Hong, WANG Qin, LIU Jing-Yao*. Theoretical Study on the Mechanism and Dynamic of CF₃CH₂CH₃ Reaction with OH Radicals[J]. Chem. J. Chinese Universities, 2010, 31(6): 1240.

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Theoretical Study on the Mechanism and Dynamic of CF₃CH₂CH₃ Reaction with OH Radicals

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