Journal
CHEMICAL PHYSICS LETTERS
Volume 323, Issue 3-4, Pages 365-371Publisher
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DOI: 10.1016/S0009-2614(00)00493-0
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Subpicosecond internal conversion dynamics of cis- and trans-1,3,5-hexatriene in cyclohexane were studied using sub 50 fs ultraviolet pulses. This time resolution allows direct observation of the 1B (S-2) and 2A (S-1) lifetimes. The 1B lifetime is 55 +/- 20 fs for trans-hexatriene, and less than or equal to 50 fs for cis-hexatriene. The subsequent 2A lifetime of trans-hexatriene is found to be 190 +/- 30.fs, and is controlled by the rate of intramolecular vibrational energy redistribution. The 2A lifetime in cis-hexatriene is 250 +/- 30 fs, and is affected by modification of the excited state potential energy surface from coupling with the solvent. (C) 2000 Elsevier Science B.V. All rights reserved.
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