Canonical Variational Transition-State Theory Study of the CF3CH2CH3 + OH Reaction

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• 作者：À ; ngels Gonz&aacute ; lez-Lafont ; José ; M. Lluch ; Adri&aacute ; n Varela-&Aacute ; lvarez ; José ; A. Sordo
• 刊名：Journal of Physical Chemistry B
• 出版年：2008
• 出版时间：January 17, 2008
• 年：2008
• 卷：112
• 期：2
• 页码：328 - 335
• 全文大小：227K
• 年卷期：v.112,no.2(January 17, 2008)
• ISSN：1520-5207

文摘

Variational transition-state theory rate constants with multidimensional tunneling contributions using the smallcurvature method have been calculated for the CF₃CH₂CH₃ (HFC-263fb) + OH reaction over a temperaturerange from 200 to 373 K. The mPW1B95-41.0 hybrid functional, parametrized by Albu and Swaminathan togenerate theoretical rate constants nearly identical to the experimental values for the CH₃F + OH reaction,has been used in conjunction with the 6-31+G** basis set to explore the potential energy surface of the titlereaction. The good agreement found between theoretical predictions and the experimental data available suggeststhat the present approach is an excellent option to obtain high-quality results at low computational cost fordirect dynamics studies of hydrogen abstraction reactions from complex hydrofluorocarbons. The reliabilityof the structure activity relationship used to estimate rate constant values for OH reactions withhydrofluorocarbons is also discussed in detail.