Abstract

Elimination of the excited hydrogen atoms H(n), n = 4–7, and hydrogen migration in formation of the excited NH(A3Π) free radicals in the photodissociation of pyridine, C5H5N, molecules have been studied over the 17.5–70 eV photon energy range. In the measurements the photon-induced fluorescence spectroscopy technique has been applied. Both fragments are produced through excitation of pyridine molecules into higher-lying superexcited Rydberg or doubly excited states. The mechanisms for fragmentation of pyridine into H(n) and NH(A3Π) are discussed. Ab initio quantum chemical calculations have been performed to elucidate the hydrogen migration mechanism in the NH formation, which is not a self-contained unit in the structure of pyridine.

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