Ab initio direct dynamics studies on the hydrogen abstraction reactions of CF2H2 and CF3H with F atom

作者：Wang, Li; Liu, Jing-Yao^*; Li, Ze-Sheng

来源：Chemical Physics, 2008, 351(1-3): 154-158.

DOI：10.1016/j.chemphys.2008.04.011

• ab initio
• rate constant
• variational transition state theory

The dynamic properties of the hydrogen abstraction reactions of CF2H2 and CF3H with F atom are investigated in the temperature range of 182-2000 K. The minimum-energy path (MEP) is optimized at MP2/ 6-311 G(d, p) level, then the energy profiles are refi tied at the CCSD(T)/6-311++G(3df, 2pd) level (singlepoint). The theoretical rate constants, which are calculated by the variational transition state theory (VrST) including the small curvature tunneling (SCT) correction, are in good agreement with the experimental ones. It is found that the rate constant of the CF2H2 + F reaction are larger than that of the CF3H + F reaction and the activation energies exhibit in the just opposite order. This phenomenon can be rationalized by the hardness il of the halomethane molecules. The comparison of the two reactions with the CFH3 + F reaction is made. It is found that the rate constants decrease in the order of CFH3 + F > CF2H2 + F > CF3H + F. The effect of fluorine substitution leads to a dramatic increase in the activation energy and a decrease in the preexponential factor. We hope that present theoretical studies for these compounds can give further information concerning how fluorine substitution affects the rate constants of hydrogen abstraction reactions.

• 出版日期2008-7-3
• 单位吉林大学