Vibronic coupling of pyrene in the first P-P-star excited state

Year: 1984

Authors: Salvi P.R., Castellucci E., Foggi P., Quacquarini R.

Autors Affiliation: Dipartimento di Chimica, Università di Firenze, Via G. Capponi 9, 50121 Florence, Italy

Abstract: The two-photon fluorescence excitation spectrum of pyrene in n-hexane and n-heptane matrices has been measured at 10 K in the region of the first electronic transition (26800-30200 cm-1). The spectrum consists of a rich number of sharp bands, being in general better resolved in n-hexane than in n-heptane matrix. Shpol\’skii multiplets have been observed for the most intense bands. A strong two-photon band dominates the spectrum = 1495 cm-1 from the 0-0 line and was assigned to B1u × b1u = Ag symmetry. Other weaker vibronic origins occur in the spectrum which were correlated to vibrational modes of b1u, b2u, b3u and au symmetry. Intense vibronic bands are observed close to the origin of the second electronic transition and were interpreted as combination bands of B1u × b1u × b3g symmetry. A two-photon vibronic theory to account for their intensity is proposed where the electronic moment is linearly expanded in powers of the nuclear displacements.

Journal/Review: CHEMICAL PHYSICS

Volume: 83 (3)      Pages from: 345  to: 356

KeyWords: pyrene
DOI: 10.1016/0301-0104(84)85010-7

Citations: 11
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