A THEORETICAL TREATMENT OF THE PREDISSOCIATION OF THE INDIVIDUAL ROVIBRONIC LEVELS OF OH OD(A2-SIGMA+)

The electronic structure aspects of the radiationless decay of the A (2)SIGMA+ state of OH/OD are considered using large scale configuration interaction (CI) (590 000-750 000 configuration state functions) wave functions and the full microscopic Breit-Pauli interaction. The A (2)SIGMA+ approximately ((4)-SIGMA-, (2)SIGMA-, (4)PI) spin-orbit induced perturbations are reported for 1.25 less-than-or-equal-to R less-than-or-equal-to 10 a0. These perturbations are used to determine the total decay rates (radiative plus radiationless decay) within a Fermi golden rule approximation. Excellent agreement with the available experimental data is found.