The asymptotic region of the potential energy surfaces relevant for the O(3P)+O2(X 3Σg−)⇌O3 reaction

The potential energy functions for all states of ozone correlating with the lowest O(3P)+O2(X 3Σg−) asymptote have been calculated in the asymptotic region employing correlated electronic wave functions. For linear ozone, the Σs states (s=1,3, and 5) lie above the corresponding Πs states. For bent geometries the Π states split into Renner–Teller components with A′ and A″ symmetry, respectively. While the Π1 and Π3 states lead to bent–bent Renner–Teller pairs, the Π5 state gives rise to a linear/linear pair of states. The different spin multiplets emerging from the Π states cross for valence angles around 160° and the A′1 component becomes the lowest one. The matrix elements of the spin-orbit operator have also been calculated. They are dominated by the atomic P3 contributions and their dependence on the mutual orientation of the O2 molecule and the O atom is small. In the regions where the states correlating to the linear Π1,3,5 cross, i.e., for valence angles between 150° and 180° and close to 90°, the mixing among the singlet, triplet, and quintet states is strong and the electron spin quantum number is no longer a good quantum number.