Journal of Physical Chemistry B, Vol.108, No.31, 11792-11801, 2004
Uphill energy trapping by reaction center in bacterial photosynthesis. 2. Unistep charge separation, virtually mediated by special pair, by photoexcitation in place of excitation transfer from the antenna system
In photosynthesis of purple bacteria, excitation energy of bacteriochlorophylls in the core antenna LH1 is transferred to the excited state (P*) of the special pair (P) in the reaction center (RC). Subsequently, charge separation to the adjacent monomeric bacteriochlorophyll (B) occurs from P*, producing P+B- as initial energy fixation in the RC. Although the absorption-peak energy of P is appreciably (by 200-430 cm(-1)) higher than that of the lowest excited state LH1* of LH1, these sequential events occur still at low temperatures for the energy trapping in Rhodobacter sphaeroides, while in Rhodopseudomonas viridis LH1* is unistep converted to P+B- in the RC by the superexchange mechanism due to quantum-mechanical virtual mediation by P* at low temperatures, as clarified in part I (Sumi, H. J. Phys. Chem. B 2002, 106, 13370). Such differences arise since in the free energy LH1* is slightly (by similar to50 cm(-1)) higher than P* in Rb. sphaeroides, while in Rps. viridis LH1* is still considerably (similar to150 cm(-1)) lower than P* in the free energy, after reorganization of the medium around P*. An experiment is proposed to investigate unifiedly such differences, by photoexcitation of a single RC from either Rb. sphaeroides or Rps. viridis. When the photon energy E is higher than about the free energy Eo for P*, the production rate of P+B-, measurable as the rate of absorption by the RC, will be nearly equal to that by P*, measurable as its excitation spectrum, at all temperatures by the sequential mechanism. When E is considerably lower than E-0, the former will become much larger than the latter at low temperatures by the superexchange mechanism. The photoinduced production rate of P+B- mediated by P* is given as an analytic formula bridging the two limits, for analyzing such observations expected.