ROLE OF RENNER-TELLER AND SPIN-ORBIT INTERACTION IN THE REACTIVE SCATTERING OF O(P-3) ATOMS WITH CF3I MOLECULES

Reactive scattering of O(P-3) atoms with CF3I molecules has been studi ed at initial translational energies E similar to 108 and 42 kJ mol(-1 ) using supersonic beams of O atoms seeded in He buffer gas generated from rf and microwave discharge sources. At the higher initial transla tional energy, the IO scattering shows a broad peak in the forward hem isphere with respect to the initial O atom direction with a product tr anslational energy distribution shifted to higher energy than the pred iction of phase space theory. At the lower initial translational energ y, the IO scattering shows a sideways peaked component with a fraction f' similar to 0.4 of the total available energy being disposed into t ranslation and a forward and backward peaked component with a product translational energy distribution in accord with the predictions of ph ase space theory. The sideways scattering is attributed to direct reac tion over the triplet (3)A '' potential energy surface, while the forw ard and backward peaked scattering is attributed to dissociation of a persistent singlet OICF3 complex formed by intersystem crossing to the underlying (1)A' potential energy surface. The direct scattering over the triplet (3)A '' potential energy surface contributes a fraction, similar to 0.5, to the total reaction cross Section at the lower initi al translational energy, while the forward scattering at the higher in itial translational energy is dominated by direct reaction over the tr iplet (3)A '' potential energy surface. This dynamical behavior is cor related with the effect of charge transfer interaction of the form OIR- on Renner Teller splitting of the triplet potential energy surface.