Journal of Physical Chemistry, Vol.100, No.13, 5562-5569, 1996
Level Mixing and Energy Redistribution in Bacterial Photosynthetic Reaction Centers
We performed ultrafast polarized light experiments in which we pumped the 800 nm band and probed several near- and mid-IR transitions of photosynthetic reaction centers from Rhodobacter sphaeroides. Absorption into the upper excitonic level of the special pair (P-Y+) is part of this band, but it is not known whether P (Y+) behaves as a localized state or if it mixes with accessory bacteriochlorophyll (BChl) states. A calculation of the anisotropy of pump-probe signals fails to reproduce the experimental results if the localized picture is used. In fact, the transition into P-y+ has to be 4-fold intensified over a simple exciton model prediction in order to give rise to anisotropies which are consistent with the experiment. This substantial intensification is inconsistent with previous experimental results. Agreement between theory and experiment can be achieved if the P-Y+ state is mixed with excited states of accessory BChl. Stimulated emission from the lower excitonic level of the special pair (P-Y-), probed at 950 nm after pumping at 800 nm, does not appear instantaneously, but rises with a time constant of 110 fs. A novel excited state absorption of the accessory BChls at 1200 nm, assigned as a monomer transition by comparison with a pump-probe experiment on free BChl dissolved in acetone, also decays with a similar to 100 fs time constant. Although Forster energy transfer from accessory Bchl states to P-Y- can account for the fast transients, under the delocalized state picture suggested in this paper they would rather correspond to an internal conversion process from the mixed states to the P-Y- state.
Keywords:RHODOPSEUDOMONAS-VIRIDIS;SPECTROSCOPIC PROPERTIES;ELECTRON-TRANSFER;FEMTOSECOND SPECTROSCOPY;THEORETICAL-EXAMINATION;EXCITED-STATES;BACTERIOCHLOROPHYLL;BACTERIOPHEOPHYTIN;CHROMOPHORES;DYNAMICS