DISSOCIATION DYNAMICS OF CF3C(O)X COMPOUNDS (WHERE X = H, F AND CL)

Dissociation pathways of CF3C(O)H, CF3C(O)F, and CF3C(O)Cl are studied using ab initio molecular orbital theory. Equilibrium geometries and transition state structures are fully optimized. Heats of reaction and activation energies are computed by using the Moller-Plesset perturbation theory with and without annihilation of spin contamination for molecular and free radical dissociation pathways. A new primary dissociation pathway is predicted o be the most favorable reaction route to dissociation for CF3C(O)H, CF3C(O)F and CF3C(O)Cl. It is the 1,2-CF2 molecular elimination process that forms CF2 radicals and HFCO, F2CO or FClCO. In the case of CF3C(O)Cl, the extrusion of chlorine atoms to yield CF3CO radicals is the next pathway which could compete with the 1,2-CF2 elimination route.