A THEORETICAL-STUDY OF THE DECOMPOSITIONS OF CF3CO AND CF3C(O)O RADICALS

Ozone in the stratosphere is important to the life of human being and the radicals CF3CO and CF3C(O>O may play important roles in the remova l of ozone by participating in the circular catalytic reactions of the degradation of ozone. So it is essential to make clear the thermodyna mic and kinetic properties of the decomposition reactions of the two r adicals. Several experimental results had been reported on these react ions, but these results are quite different from each other. Theoretic ally, these reactions had been studied by using ab initio method at 6- 31G level and the correlation energy was considered with PMP2. In thi s paper, the thermodynamic and kinetic data of the reactions had been calculated over the temperature interval from 100 K to 1500 K based on statistical thermodynamics and transition state theory by using the d ata obtained from nb initio calculation. The thermodynamic and kinetic data of these reactions such as K-p and k(r) had been obtained. The r esult of calculation is well consistent with the latest experimental d ata and the conclusion was drawn that both CF3CO and CF3(O)O radicals are too unstable to participate in the catalytic cycles of the removal of ozone in the stratosphere.