AZULENE REVISITED - PICOSECOND DECAY OF S1 STATE IN GAS-PHASE AND IN SOLUTION
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In this paper we report the results of an experimental study of picosecond timeresolved relaxation dynamics of the S1 state of the azulene molecule in solution and in the low pressure gas phase, utilizing consecutive twophoton excitation S0 S1(v) S2 (or S3), with the exciting and the monitoring picosecond pulses chosen at the same wavelength. The nonradiative electronic relaxation times for azulene in solution were nr = 4 3 ps for S(v = 5), excited at 530 nm, and nr = 3 2 ps for S(v = 2), excited at 625 nm, while for the isolated molecule case nr = 4 3 ps for S(v = 2), excited at 625 nm. The electronic relaxation rate of the S1 manifold exhibits only a weak dependence on the excess vibrational energy Ev up to Ev = 4800 cm1. The electronic relaxation rate is practically unaffected by solvent perturbations, as appropriate for the statistical limit of intramolecular radiationless transitions. Copyright 1977 WILEYVCH Verlag GmbH & Co. KGaA, Weinheim