Spin-orbit coupling in O2„ ...+O2 collisions: I. Electronic structure

The importance of vibrational-to-electronic V-E energy transfer mediated by spin-orbit coupling in the collisional removal of O2 X 3 g − , 26 by O2 has been reported in a recent communication F. Dayou, J. Campos-Martínez, M. I. Hernández, and R. Hernández-Lamoneda, J. Chem. Phys. 120, 10355 2004 . The present work provides details on the electronic properties of the dimer O2 2 relevant to the self-relaxation of O2 X 3 g − , 0 where V-E energy transfer involving the O2 a 1 g and O2 b 1 g + states is incorporated. Two-dimensional electronic structure calculations based on highly correlated ab initio methods have been carried out for the potential-energy and spin-orbit coupling surfaces associated with the ground singlet and two low-lying excited triplet states of the dimer dissociating into O2 X 3 g − +O2 X 3 g − , O2 a 1 g +O2 X 3 g − , and O2 b 1 g +