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

Photosynth Res. 2015 Aug;125(1-2):9-22. doi: 10.1007/s11120-014-0041-5. Epub 2014 Sep 21.

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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Bacteriochlorophylls / metabolism*
  • Electron Transport
  • Kinetics
  • Models, Theoretical
  • Photosynthesis
  • Photosynthetic Reaction Center Complex Proteins / metabolism*
  • Rhodobacter sphaeroides / physiology*
  • Spectrum Analysis

Substances

  • Bacteriochlorophylls
  • Photosynthetic Reaction Center Complex Proteins