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Published April 1, 1985 | Published
Journal Article Open

Picosecond excitation and selective intramolecular rates in supersonic molecular beams. IV. Alkylanthracenes


To assess the role of alkylation on IVR, the dynamics of jet cooled 9-methyl and 9-hexylanthracene excited to single vibronic levels (SVL) in S1 are investigated and compared with the parent molecule, anthracene, whose picosecond IVR dynamics are now well characterized. Vibrations in S1 and S0 are analyzed. Decay rates and SVL fluorescence spectra are also presented. The decay rates as a function of excess vibrational energy increase rapidly at low energy but become relatively constant at high energy. The approximate energy threshold at which the decay rate "saturates" is dependent on the substitutent; anthracene ([approximately-equal-to]1800 cm^−1), 9-methylanthracene ([approximately-equal-to]1000 cm^−1), 9-hexylanthracene ([approximately-equal-to]400 cm^−1), and A–(CH2)3–[cursive phi] (<=400 cm^−1). These identified thresholds are discussed and related to IVR processes. Finally, some comments on the importance of low frequency modes to IVR are given.

Additional Information

© 1985 American Institute of Physics. Received 5 November 1984; accepted 7 December 1984. We gratefully acknowledge the support of this work by the National Science Foundation. [P.M.F. was an] IBM Predoctoral Fellow. [A.H.Z. was a] Camille and Henry Dreyfus Foundation Teacher-Scholar. Arthur Amos Noyes Laboratory of Chemical Physics; Contribution No. 7093.

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