The asymptotic region of the potential energy surfaces relevant for the O([sup 3]P)+O[sub 2](X [sup 3]Σ[sub g][sup -])⇋O[sub 3] reaction.

The potential energy functions for all states of ozone correlating with the lowest O(³P) +O[sub 2](X³Σ[sup -][sub g]) asymptote have been calculated in the asymptotic region employing correlated electronic wave functions. For linear ozone, the [sup s]Σ states (s = 1, 3, and 5) lie above the corresponding [sup s]Π states. For bent geometries the H states split into Renner-Teller components with A' and A' symmetry, respectively. While the ¹Π and ³Π states lead to bent-bent Renner-Teller pairs, the [sup 5]Π state gives rise to a linear/linear pair of states. The different spin multiplets emerging from the H states cross for valence angles around 160° and the ¹A' component becomes the lowest one. The matrix elements of the spin-orbit operator have also been calculated. They are dominated by the atomic ³p contributions and their dependence on the mutual orientation of the O[sub 2] molecule and the O atom is small. In the regions where the states correlating to the linear [sup 1,3,5]Π states 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. [ABSTRACT FROM AUTHOR]