Abstract
The electronic structure aspects of the radiationless decay of the A 2Σ+ 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 2Σ+∼(4Σ−,2Σ−,4Π) spin–orbit induced perturbations are reported for 1.25≤R≤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.
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