Subpicosecond vibrational relaxation of the S 1 ...



Title Subpicosecond vibrational relaxation of the S 1 states of azulene and guaiazulene in solution
Author(s) D. Tittelbachhelmrich, Brian D. Wagner, R. P. Steer
Journal Canadian Journal of Chemistry / Revue Canadienne De Chimie
Date 1995
Volume 73
Issue 2
Start page 303
End page 306
Abstract The S-1 population decay times of azulene and 1,4-dimethyl-7-isopropylazulene (guaiazulene) in solution have been determined as a function of their initial vibrational energy content, E(vib)(i), using a pump-probe experiment with subpicosecond time resolution. The S-1 lifetime of azulene does not depend on E(vib)(i) for energies up to 1760 cm(-1), whereas the lifetime of the shorter-lived S-1 state of guaiazulene is independent of E(vib)(i) only for energies up to similar to 1000 cm(-1). At higher energies, the lifetime decreases with increasing E(vib)(i), and exhibits the same behavior in two structurally different solvents. It is suggested that internal conversion to the electronic ground state from a vibrationally unrelaxed S-1 state is responsible for the effects observed in guaiazulene, and that intramolecular vibrational redistribution occurs with a time constant of several hundred femtoseconds.

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