HUND'S CASE (a)-CASE (b) TRANSITION IN THE SINGLET-TRIPLET SPECTRUM OF PRYAZINE IN A SUPERONIC $JET,^{*}$

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1996

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Ohio State University

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We report theoritical calculations of the $T_{1}-S_{0}$ excitation spectrum of pyrazine, pyrazine-$d_{4}$, and the pyrazine-Arvan der Waals complex. Towards this end, a closed analytical formula for the intensities of individual rovibronic transitions has been derived. The triplet state Hamiltonian includes, in addition to the usual rigid rotor terms, both intramanifold spin-spin coupling and intermanifold spin-orbit coupling. Taking reasonable values for these parametres leads to several experimental predictions, including a transition from Hund#### Case (a) to Case (b) with increasing J and the apperance of fine structure splittings at even moderate spectral resolution. Detailed examples will be discussed.

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$^{*}$ Work supported by the U.S. NAS/NRC CAST Program, by the U.S. National Science Foundation (CHE-9224398), by the International Science Foundation (SDQ000, NJ6000, NJ6300), and by the Russian Foundation for Basic Research (95-03-08 130a)
Author Institution: Institute of Chemical Physics, Russian Academy of Sciences; Department of Chemistry, University of Pitsburgh

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