Citation: CUI Feng-Chao, YU Hong-Bo, WANG Qin, YE Wan-Li, LIU Jing-Yao. Mechanism and Kinetics of the CH₃OCF₂CF₂OCH₃+Cl Reaction[J]. Acta Physico-Chimica Sinica, ;2011, 27(02): 337-342. doi: 10.3866/PKU.WHXB20110201 shu

Mechanism and Kinetics of the CH₃OCF₂CF₂OCH₃+Cl Reaction

1.
State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, P. R. China

Received Date: 27 September 2010
Available Online: 15 December 2010
Fund Project: 国家自然科学基金(20333050, 20303007, 20973077) (20333050, 20303007, 20973077)教育部新世纪优秀人才支持计划(NCET)资助项目 (NCET)

A direct density functional theory dynamics method was used to determine the mechanism and kinetics of the CH₃OCF₂CF₂OCH₃+Cl reaction. Potential energy surface information was obtained at the BB1K/6-31+G(d,p) level. The hydrogen abstraction channels and displacement processes of the two stable conformers (SC1 and SC2) of CH₃OCF₂CF₂OCH₃ were taken into consideration. Theoretical rate constants of the individual H-abstraction channels (one from SC1 and two from SC2) were calculated by improved canonical variational transition state theory (ICVT) with a small-curvature tunneling (SCT) correction. The overall rate constant (k_T) was obtained by considering the weight factor of each conformer from the Boltzmann distribution function and the contribution of the two conformers to the whole reaction was discussed. The calculated k_T(ICVT/SCT) at 296 K agrees well with the experimental value. Since experimental data were lacking for other temperatures, a three-parameter rate constant temperature expression for the total reaction within 200-2000 K was fitted to: k_T=0.40×10^-14T^1.05exp(-206.16/T).
- Density functional theory,
- Direct dynamics,
- Rate constant,
- Improved canonical variational transition state theory,
- CH₃OCF₂CF₂OCH₃
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沈阳化工大学材料科学与工程学院沈阳 110142

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Mechanism and Kinetics of the CH₃OCF₂CF₂OCH₃+Cl Reaction