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

The state specific predissociation of OH/OD in its lowest electronically ex cited state (A (2)Sigma (+), nu', N', F-1/F-2) is investigated by time depe ndent wave packet propagation techniques. To improve the accuracy of the po tential energy curves, spin-orbit, spin-spin and rotational interactions re quired 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 exper iment and with theoretical values from multichannel scattering theory.