Abstract

Vibrational relaxation in the 2Ag- (S1) state of all-trans-lycopene, which takes place in a time scale slower than that of internal conversion, has been found by picosecond time-resolved absorption spectroscopy: The time-resolved Sn (2Bu+) ← S1 (2Ag-) absorption spectra of this carotenoid in quinoline and CS2 solutions can be explained in terms of vibrational structures originating from the CC (ν1) and C−C (ν2) stretching modes, and the time scales of vibrational relaxation (kν1 and kν2 defined for the lowest vibrational transition) relative to that of internal conversion (k) are estimated by spectral simulation; the values of kν1/k and kν2/k are around 0.6 and 0.3 in the quinoline solution and 0.2 and 1.6 in the CS2 solution. The slower vibrational relaxations are discussed in light of the light-harvesting function of carotenoids in photosynthesis.

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