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Reaction-path dynamics and theoretical rate constants for the CH(n)F(4-n) + O3 --> HOOO + CH(n-1)F(4-n) (n = 2,3)
Qian Shu Li1, Jing Yang, Shaowen Zhang
1School of Chemistry and Environment, South China Normal University, Guangzhou 510006, People's Republic of China. qsli@bit.edu.cn
Abstract:
We present a theoretical study of the hydrogen abstraction reactions from CH(3)F and CH(2)F(2) by an ozone molecule. The geometries and harmonic vibrational frequencies of all stationary points are calculated at the MPW1K, BHandHLYP, and MPWB1K levels of theory. The energies of all of the stationary points were refined by using both higher-level (denoted as HL) energy calculations and QCISD(T)/6-311++G(2df,2pd) calculations based on the optimized geometries at the MPW1K/6-31+G(d,p) level of theory. The minimum energy paths (MEPs) were obtained by the MPW1K/6-31+G(d,p) level of theory. Energetic information of the points along the MEPs is further refined by the HL method. The rate constants were evaluated on the basis of the MEPs from the HL level of theory in the temperature range 200-2500 K by using the conventional transition-state theory (TST), the canonical variational transition-state theory (CVT), the microcanonical variational transition-state theory (microVT), the CVT coupled with the small-curvature tunneling (SCT) correction (CVT/SCT), and the microVT coupled with the Eckart tunneling correction (microVT/Eckart) based on the ab initio calculations. A general agreement was found among the TST, CVT, and microVT theories. The fitted three-parameter Arrhenius expressions of the calculated forward CVT/SCT and microVT/Eckart rate constants of the ozonolysis of fluoromethane are k(CVT/SCT)(T) = 2.76 x 10(-34)T(5.81)e((-13975/)(T)) and k(microVT/Eckart)(T) = 1.15 x 10(-34)T(5.97)e((-14530.7/)(T)), respectively. The fitted three-parameter Arrhenius expressions of the calculated forward CVT/SCT and microVT/Eckart rate constants of the ozonolysis of difluoromethane are k(CVT/SCT)(T) = 2.29 x 10(-36)T(6.42)e((-15451.6/)(T)) and k(microVT/Eckart)(T) = 1.31 x 10(-36)T(6.45)e((-15465.8/)(T)), respectively.
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