Abstract
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.
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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.
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Medvedev, E.S., Pratt, D.W. Hund’s Case (a)-case (b) transition in the singlet-triplet absorption spectrum of pyrazine in a supersonic jet. J. Exp. Theor. Phys. 87, 35–50 (1998). https://doi.org/10.1134/1.558642
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DOI: https://doi.org/10.1134/1.558642