Spin-dependent and Coriolis interactions by an improved configuration interaction treatment: predissociation of excited fine structure levels of OH/OD

Abstract

The state specific predissociation of OH/OD in its lowest electronically excited state (A (2)Sigma (+), nu', N', F-1/F-2) is investigated by time dependent wave packet propagation techniques. To improve the accuracy of the potential energy curves, spin-orbit, spin-spin and rotational interactions required for the treatment, we have refined our CI techniques, using optimal orbitals for each of the electronic states. Potential energy curves, matrix elements and lifetimes of the rotational sublevels are compared with experiment and with theoretical values from multichannel scattering theory.