Photosynthetic electron transfer controlled by protein relaxation: Analysis by Langevin stochastic approach

Relaxation processes in proteins range in time from picoseconds to seconds. Correspondingly, biological electron transfer (ET) could be controlled by slow protein relaxation. We used the Langevin stochastic approach to descri be this type of ET dynamics. Two different types of kinetic behavior were r evealed, namely: oscillating ET (that could occur at picoseconds) and monot onically relaxing ET. On a longer time scale, the ET dynamics can include t wo different kinetic components. The faster one reflects the initial, nonad iabatic ET, whereas the slower one is governed by the medium relaxation. We derived a simple relation between the relative extents of these components , the change in the free energy (DeltaG), and the energy of the slow reorga nization A. The rate of ET was found to be determined by slow relaxation at -DeltaG less than or equal to Lambda. The application of the developed app roach to experimental data on ET in the bacterial photosynthetic reaction c enters allowed a quantitative description of the oscillating features in th e primary charge separation and yielded values of A for the slower low-exot hermic ET reactions. In all cases but one, the obtained estimates of Lambda varied in the range of 70-100 meV. Because the vast majority of the biolog ical ET reactions are only slightly exothermic (DeltaG greater than or equa l to -100 meV), the relaxationally controlled ET is likely to prevail in pr oteins.