Canonical Variational Transition-State Theory Study of the CF3CHFCH2F + OH Reaction

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• 作者：ngels Gonzlez-Lafont ; Jos M. Lluch ; Adrin Varela-lvarez ; Jos A. Sordo
• 刊名：Journal of Physical Chemistry A
• 出版年：2010
• 出版时间：March 4, 2010
• 年：2010
• 卷：114
• 期：8
• 页码：2768-2777
• 全文大小：350K
• 年卷期：v.114,no.8(March 4, 2010)
• ISSN：1520-5215

文摘

Variational transition-state theory rate constants with multidimensional tunneling contributions using the small curvature method have been calculated for the CF₃CHFCH₂F (HFC-245eb) + OH reaction over a temperature range from 200 to 800 K. The mPW1B95−41.0 hybrid functional, parametrized by Albu and Swaminathan to generate theoretical rate constants nearly identical to the experimental values for the CH₃F + OH reaction, has been used in conjunction with the 6-31+G(d,p) basis set to explore the potential energy surface of the title reaction. The functional provides results within the limits of chemical accuracy, supporting the conclusions about transferability of a previous study on the CF₃CH₂CH₃ + OH reaction. Fourteen different reaction channels have been explored, all of them with significant contributions to the global rate constants.