| Abstract
| - This investigation was motivated by a desire to get a deeper insight into the mechanism of carotenoiod-to-bacteriochlorophyll (Car-to-BChl) energy transfer proceeding via the carotenoid S1 state. (Here, we call the2Ag- and 1Bu+ states “the S1 and S2 states” according to the notation presently accepted.) To systematicallyexamine the effect of the conjugation length of carotenoid on the rate and efficiency of the Car(S1)-to-BChl(Qy) energy transfer, we performed the following experiments. (1) Subpicosecond time-resolved absorptionspectroscopy was employed to measure the S1-state lifetimes of lycopene (number of conjugated CC bonds,n = 11), spheroidene (n = 10), and neurosporene (n = 9), both free in n-hexane and bound to the LH2complexes from Rhodospirillum molischianum (Rs. molischianum), Rhodobactor sphaeroides (Rb. sphaeroides)2.4.1, and Rb. sphaeroides G1C, respectively. The lifetime of each free (bound) carotenoid was determinedto be 4.7(3.4) ps for lycopene, 9.3(1.7) ps for spheroidene, and 21.2(1.3) ps for neurosporene. It was foundthat the rate and the efficiency of the Car(S1)-to-BChl(Qy) energy transfer increase systematically when thenumber of conjugated CC bonds decreases. (2) High-sensitivity steady-state fluorescence spectroscopy wasused to measure the spectra of dual emission from the S2 and S1 states for the above carotenoids dissolvedin n-hexane. The fluorescence data, combined with the above kinetic data, allowed us to evaluate the magnitudesof the transition-dipole moments associated with the Car(S1) emission. It was found that the S1 emissions ofthe above carotenoids carry noticeably large oscillator strengths (transition-dipole moments). In the case ofthe LH2 complex from Rs. molischianum, whose structural information is now available, the time constantof the Car(S1)-to-BChl(Qy) energy transfer (18.6 ps), which was predicted on the basis of a Car(S2)-to-BChl(Qy) full Coulombic coupling scaled by the ratio of the S1 vs S2 transition dipole moments, was in goodagreement with the one spectroscopically determined (12.3 ps). The oscillator strength associated with theCar(S1) emission was discussed in terms of the state mixing between the carotenoid S2 and S1 states.
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