Canonical variational transition-state theory study of the CF3CH2CH3 + OH reaction.
Variational transition-state theory rate constants with multidimensional tunneling contributions using the small curvature method have been calculated for the CF3CH2CH3 (HFC-263fb) + OH reaction over a temperature range from 200 to 373 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** basis set to explore the potential energy surface of the title reaction. The good agreement found between theoretical predictions and the experimental data available suggests that the present approach is an excellent option to obtain high-quality results at low computational cost for direct dynamics studies of hydrogen abstraction reactions from complex hydrofluorocarbons. The reliability of the structure activity relationship used to estimate rate constant values for OH reactions with hydrofluorocarbons is also discussed in detail.
Gonzalez-Lafont
Angels
A
Departament de Química, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona, Spain. angels@klingon.uab.es
Lluch
José M
JM
Varela-Alvarez
Adrian
A
Sordo
José A
JA