Spin-orbit induced predissociation of the B2Σ-g and 22Σg+ states of the O2+ ion

Highly correlated MRCI electronic wavefunctions are used to calculate the potential energy functions, the non-adiabatic and the spin-orbit coupling elements for the B(2)Sigma(g)(-) and neighboring states of the O-2(+) ion. The results are employed in calculations of the spectroscopic constants and the spin-orbit induced predissociation lifetimes using the complex scaling method. The dominant predissociation path correlating with the O+O+ atoms in their ground states is found to proceed via the f(4)Pi(g) state. The path leading to the O(D-1) + O+(S-4) asymptote involves couplings with the 2(2)Pi(g) and 2(4)Pi(g) states. The weak vibrational progression embedded in the progression of the B-state is assigned to the 2(2)Sigma(g)(+) state. The predissociative lifetimes are calculated to be distinctly longer than the apparent experimental lifetimes reported previously. (C) 2003 Elsevier B.V. All rights reserved.