AN EXAMINATION OF PATHWAYS FOR THE REACTION OF OXYGEN-ATOMS WITH CF3O RADICALS - IMPLICATIONS FOR THE ROLE OF CF3 RADICALS IN STRATOSPHERIC CHEMICAL PROCESSES

The reaction of CF3o (X 2A') with O (P-3) has been studied using ab initio molecular orbital theory. The study shows that the products for this reaction are surface dependent. If the reaction proceeds along the 2A'' surface, the expected products will be CF3(X 2A1) and O2(3SIGMA(g)-). If the reaction proceeds along the 2A' surface the only expected product will be excited state CF3O2(2A') radicals. The reactions leading to the formation of CF2O(X 1A1) and FO(2PI) have activation energies of 16.4 and 40.9 kcal mol -1 on the 2A' and 2A'' surfaces, respectively, and hence are not favored processes kinetically. The detailed chemical dynamics of this reaction and its atmospheric chemical implications are discussed.