Direct dynamics studies on the hydrogen abstraction reactions CF 3O+CH 4(CD 4)→CF 3OH(CF 3OD)+CH 3(CD 3)

Abstract

The dynamics properties of the hydrogen abstraction reaction CF 3O+CH 4→CF 3OH+CH 3 are studied by dual-level direct dynamics method. Optimization calculations are preformed by B3LYP and MP2 with the 6-311G(d,p) basis set, and the single-point calculations are done at the multi-coefficient correction method based on quadratic configuration interaction with single and double excitations (MC-QCISD) method. The rate constants are evaluated by canonical variational transition-state theory with a small-curvature tunneling correction over a wide range of temperature 200–2000 K. The agreement between theoretical and experimental rate constants is good in the measured temperature range. The calculated results show that the variational effect is small and almost neglected over the whole temperature range, whereas, the tunneling correction plays a role in the lower temperature range. The kinetic isotope effect for the reaction is ‘normal’. The value of k H/ k D is 2.38 at room temperature and it decreases with the temperature increasing.