Sr. Davis et Ba. Yu, AB-INITIO STUDY OF THE CATALYTIC DECOMPOSITION OF TETRAFLUOROETHYLENEBY MOLECULAR-OXYGEN, Journal of physical chemistry, 100(27), 1996, pp. 11276-11281
The reaction of tetrafluoroethylene with molecular oxygen was consider
ed as the following three-step process: TFE + O-2 --> C2F4OO --> CF2 CF2OO --> 2CF(2) + O-2, with the overall reaction being C2F4 + O-2 --
> 2CF(2) + O-2. The equilibrium geometries and vibrational frequencies
were determined for all reactants, products, and transition states, a
s well as activation energies and reaction enthalpies. Geometries were
obtained at the MP2/6-311G(d) level while energies were computed at t
he MP4SDTQ/6-311G(d)//MP2/6-311G(d) computational level. The (CF2)-C-.
-CF2OO. biradical was characterized for the first time and found to be
long to the C-s point group and the (3)A '' ground electronic state. T
he equilibrium geometry for the (CF2OO.)-C-. biradical, in the (3)A st
ate, was determined and found to belong to point group C-1. The second
step was found to be rate determining with an activation energy of 54
.0 kcal/mol. The overall reaction enthalpy of 62.7 kcal/mol agrees wel
l with the experimental value of 66 kcal/mol.