Spectroscopic Properties of Reaction Center Pigments in Photosystem II Core Complexes: Revision of the Multimer Model

AbstractAbsorbance difference spectra associated with the light-induced formation of functional states in photosystem II core complexes from Thermosynechococcus elongatus and Synechocystis sp. PCC 6803 (e.g., P+Pheo−,P+QA−,3P) are described quantitatively in the framework of exciton theory. In addition, effects are analyzed of site-directed mutations of D1-His198, the axial ligand of the special-pair chlorophyll PD1, and D1-Thr179, an amino-acid residue nearest to the accessory chlorophyll ChlD1, on the spectral properties of the reaction center pigments. Using pigment transition energies (site energies) determined previously from independent experiments on D1-D2-cytb559 complexes, good agreement between calculated and experimental spectra is obtained. The only difference in site energies of the reaction center pigments in D1-D2-cytb559 and photosystem II core complexes concerns ChlD1. Compared to isolated reaction centers, the site energy of ChlD1 is red-shifted by 4nm and less inhomogeneously distributed in core complexes. The site energies cause primary electron transfer at cryogenic temperatures to be initiated by an excited state that is strongly localized on ChlD1 rather than from a delocalized state as assumed in the previously described multimer model. This result is consistent with earlier experimental data on special-pair mutants and with our previous calculations on D1-D2-cytb559 complexes. The calculations show that at 5K the lowest excited state of the reaction center is lower by ∼10nm than the low-energy exciton state of the two special-pair chlorophylls PD1 and PD2 which form an excitonic dimer. The experimental temperature dependence of the wild-type difference spectra can only be understood in this model if temperature-dependent site energies are assumed for ChlD1 and PD1, reducing the above energy gap from 10 to 6 nm upon increasing the temperature from 5 to 300K. At physiological temperature, there are considerable contributions from all pigments to the equilibrated excited state P*. The contribution of ChlD1 is twice that of PD1 at ambient temperature, making it likely that the primary charge separation will be initiated by ChlD1 under these conditions. The calculations of absorbance difference spectra provide independent evidence that after primary electron transfer the hole stabilizes at PD1, and that the physiologically dangerous charge recombination triplets, which may form under light stress, equilibrate between ChlD1 and PD1