Triplet State Energy Transfer Between the Primary Donor and the Carotenoid in Rhodobacter sphaeroides R‐26.1 Reaction Centers Exchanged with Modified Bacteriochlorophyll Pigments and Reconstituted with Spheroidene

Abstract— The dynamics of triplet energy transfer between the primary donor and the carotenoid were measured on several photosynthetic bacterial reaction center preparations from Rhodobacter sphaeroides: (a) wild‐type strain 2.4.1, (b) strain R‐26.1, (c) strain R‐26.1 exchanged with 132‐hy‐droxy‐[Zn]‐bacteriochlorophyll at the accessory bacteriochlorophyll (BChl) sites and reconstituted with spheroidene and (d) strain R‐26.1 exchanged with P‐vinyl]‐132‐hydroxy‐bacteriochlorophyll at the accessory BChl sites and reconstituted with spheroidene. The rise and decay times of the primary donor and carotenoid triplet‐triplet absorption signals were monitored in the visible wavelength region between 538 and 555 run as a function of temperature from 4 to 300 K. For the samples containing carotenoids, all of the decay times correspond well to the previously observed times for spheroidene (5 ± 2 us). The rise times of the carotenoid triplets were found in all cases to be biexponen‐tial and comprised of a strongly temperature‐dependent component and a temperature‐independent component. From a comparison of the behavior of the carotenoid‐con‐taining samples with that from the reaction center of the carotenoidless mutant Rb. sphaeroides R‐26.1, the temperature‐independent component has been assigned to the buildup of the primary donor triplet state resulting from charge recombination in the reaction center. Arrhenius plots of the buildup of the carotenoid triplet states were used to determine the activation energies for triplet energy transfer from the primary donor to the carotenoid. A model for the process of triplet energy transfer that is consistent with the data suggests that the activation barrier is strongly dependent on the triplet state energy of the accessory BChl pigment, BChlB.