In order to understand the origin of ultrafast carotenoid bandshifts upon photoexcitation of bacteriochlorophyll (BChl) molecules in antenna complexes of photosynthetic purple bacteria, we have performed sa-CASSCF(8,7)/6-31G (and 6-31G*) calculations for the low-lying excited states of the carotenoid rhodopin glucoside (RG). The LH2 environment was simulated via atomic point charges to represent the electrostatic field of the ground and the Q y excited states of BChls near the carotenoid. The calculations showed that excitation of the B800 BChls yields a significant blue-shift of the carotenoid S 2 energy in good agreement with experiments. We also found that the lowest triplet state energy of the RG is below 0.78 eV, which is lower than the energy of 1 O 2 * (0.97 eV), in accord with the role of carotenoids as photoprotectors.
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