Quantum chemical simulations of excited-state absorption spectra of photosynthetic bacterial reaction center and antenna complexes.

The semiempirical ZINDO/S CIS configuration interaction method has been used to study the ground- and excited-state absorption spectra of wild type and heterodimer M202HL reaction centers from purple bacterium Rhodobacter sphaeroides as well as of peripheral LH2 and LH3 light harvesting complexes from purple bacterium Rhodopseudomonas acidophila. The calculations well reproduce the experimentally observed excited-state absorption spectra between 1000 and 17,000 cm(-1), despite the necessarily limited number of chromophores and protein subunits involved in the calculations. The electron density analysis reveals that the charge transfer between adjacent chromophores dominates the excited-state absorption spectra. Clear spectroscopic differences observed between the wild type and heterodimer reaction centers as well as between the LH2 and LH3 antenna complexes arise from differences in the energy level manifolds of the complexes, particularly those of the charge transfer states. The calculations also imply that the lowest excited state of the bacterial reaction centers has charge transfer character that is related to charge transfer within the special pair and between the special pair and the accessory bacteriochlorophyll of the photosynthetically active electron transfer branch.