The asymptotic region of the potential energy surfaces relevant for the O(~3P)+O_2(X~3SIGMA_g~-) = O_3 reaction

摘要

The potential energy functions for all states of ozone correlating with the lowest O(~3P)+O_2(X~3SIGMA_g~-) asymptote have been calculated in the asymptotic region employing correlated electronic wave functions. For linear ozone, the ~sSIGMA states (s=1,3, and 5) lie above the corresponding ~sII states. For bent geometries the II states split into Renner-Teller components with A' and A" symmetry, respectively. While the ~1II and ~3II states lead to bent-bent Renner-Teller pairs, the ~5II state gives rise to a linear/linear pair of states. The different spin multiplets emerging from the II states cross for valence angles around 160 deg 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_2 molecule and the O atom is small. In the regions where the states correlating to the linear ~1,3,5II states cross, i.e., for valence angles between 150 deg and 180 deg and close to 90 deg, the mixing among the singlet, triplet, and quintet states is strong and the electron spin quantum number is no longer a good quantum number.