Journal of Chemical Physics p. 4860 - 4868 (1992)
Update date:2022-08-11
Topics:
Buma, Wybren Jan
Kohler, Bryan E.
Nuss, John M.
Shaler, Thomas A.
Song, Kyuseok
We report vibrationally resolved S0 -> S1 excitation spectra and vibronic level decay times for the phenyl-substituted polyenes 1-phenylbutadiene and 1-phenylhexatriene seeded in supersonic He expansions.This information was obtained using one- and two-color resonance-enhanced multiphoton ionization techniques.The shift in the excitation energy of the lowest excited singlet state upon deuteration of the phenyl ring demonstrates that in 1- phenylbutadiene S1 is mainly an excitation of the benzene ring while in 1-phenylhexatriene S1 is mainly the 21Ag stateof hexatriene.Analysis of the excitation spectrum of 1-phenylhexatriene shows that the spectrum contains contributions from two species, the trans,trans and the trans,cis isomers, whose 21Ag state excitation energies differ by about 155 cm-1.The lifetimes of 21Ag zero-point levels and, in particular, the activity of the C-C and C=C stretch vibrations are markedly different for the two isomers.From these results we obtain a picture of the influence that the phenyl group has on such aspects of the electronic structure of the 21Ag state of hexatriene as the effective conjugation length, the symmetry properties, and the fluorescence quantum yield.
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