Dynamics of the Excited State in Photosynthetic Bacterial Reaction Centers

In the initial charge-separation reaction of photosynthetic bacterial reaction centers, a dimer of strongly interacting bacteriochlorophylls (P) transfers an electron to a third bacteriochlorophyll (B-L). It has been suggested that light first generates an exciton state of the dimer and that an electron then moves from one bacteriochlorophyll to the other within P to form a charge-transfer state (PL+PM-), which passes an electron to B-L. This scheme, however, is at odds with the most economical analysis of the spectroscopic properties of the reaction center and particularly with the unusual temperature dependence of the long-wavelength absorption band. The present paper explores this conflict with the aid of a simple model in which exciton and charge-transfer states are coupled to three vibrational modes. It then uses a similar model to show that the main experimental evidence suggesting the formation of PL+PM- as an intermediate could reflect pure dephasing of vibrational modes that modulate stimulated emission.