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Spectral exhibition of electron-vibrational relaxation in P* state of Rhodobacter sphaeroides reaction centers

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Abstract

Electron-vibrational relaxation in the excited state of the primary electron donor, bacteriochlorophyll dimer P, in the reaction centers (RCs) of purple photosynthetic bacteria Rhodobacter sphaeroides is modeled. A multimode model of three states (i.e., the ground state Pg, initially excited P1*, and relaxed excited P2*) is used to calculate the incoherent dynamics of the difference (ΔA) spectra on a femtosecond timescale for the YM210 W mutant RCs. The relaxation processes are described by the step-ladder model. The model shows that the electron-vibrational relaxation in the excited state of P is visualized by the transient red shift of the stimulated emission from P*. The dynamics of this shift is observed as a change in the ΔA spectrum shape in its red-most part, within a few hundreds of femtoseconds after excitation. As a result, an initial rise in the red-side ΔA kinetics is delayed with respect to the blue-side kinetics. The time constant of the P1* → P2* electronic relaxation (54 fs) and the Pg, P1*, and P2* vibrational relaxations (120 fs), used in the model, provided the best fit of the experimental time-resolved ΔA spectra and kinetics at 90 and 293 K. The possible nature of the P1* → P2* electronic relaxation is discussed.

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Acknowledgments

We would like to thank Dr. L. G. Vasilieva and Dr. A. Ya. Shkuropatov, who helped to prepare the RC samples. This work is partly supported by the Russian Foundation for Basic Research (Grant No 14-04-00295a).

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  1. Belozersky Institute of Physico-Chemical Biology, Lomonosov Moscow State University, Leninskie Gory, 119991, Moscow, Russia

    Andrei G. Yakovlev

  2. Institute of Basic Biological Problems, Russian Academy of Sciences, 142290, Pushchino, Moscow region, Russia

    Vladimir A. Shuvalov

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  1. Andrei G. Yakovlev
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Correspondence to Andrei G. Yakovlev.

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Yakovlev, A.G., Shuvalov, V.A. Spectral exhibition of electron-vibrational relaxation in P* state of Rhodobacter sphaeroides reaction centers. Photosynth Res 125, 9–22 (2015). https://doi.org/10.1007/s11120-014-0041-5

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