Hund’s Case (a)-case (b) transition in the singlet-triplet absorption spectrum of pyrazine in a supersonic jet

An analytic expression is derived for calculating the intensities of individual spin-rovibronic lines in the fully resolved gas phase electronic spectrum of a polyatomic molecule, in which one of the zero-order electronic states is a triplet state. The expression is employed to calculate the effect of fine structure splitting on the singlet-triplet absorption spectrum of pyrazine using the parameters available from experiment. A transition from Hund’s coupling Case (a) to Case (b) on going from low J to high J rotational levels is predicted to occur at a moderate resolution of a few hundred MHz. The effect is more pronounced in pyrazine-d ₄ and the pyrazine-argon van der Waals complex owing to their larger mass. Zh. éksp. Teor. Fiz. 114, 63–90 (July 1998) Published in English in the original Russian journal. Reproduced here with stylistic changes by the Translation Editor.