Spin–orbit induced predissociation of the B2Σg− 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 B2Σg− and neighboring states of the O2+ 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 f4Πg state. The path leading to the O(1D) + O+(4S) asymptote involves couplings with the 22Πg and 24Πg states. The weak vibrational progression embedded in the progression of the B-state is assigned to the 22Σg+ state. The predissociative lifetimes are calculated to be distinctly longer than the apparent experimental lifetimes reported previously.