Energy Transfer and Exciton Coupling in Isolated B800−850 Complexes of the Photosynthetic Purple Sulfur Bacterium<i>Chromatium tepidum</i>. The Effect of Structural Symmetry on Bacteriochlorophyll Excited States

Abstract

Energy transfer and exciton coupling in isolated B800−850 complexes from the purple sulfur bacterium Chromatium tepidum were studied by means of spectrally resolved absorbance difference spectroscopy with a time resolution of 200 fs. Energy transfer from bacteriochlorophyll (BChl) 800 to BChl 850 was found to occur with a time constant of 0.8−0.9 ps. Remarkably, the amplitude of the absorbance changes of BChl 850 was 4 times larger than that of BChl 800. By relating this result to the crystal structure of B800−850 complexes of Rhodopseudomonas acidophila (MacDermott, G.; Prince, S. M.; Freer, A. A.; Hawthornthwaite-Lawless, A. M.; Papiz, M. Z.; Cogdell, R. J.; Isaacs; N. W. Nature 1995, 374, 517), it was concluded that the spectral properties of BChl 850 are mainly determined by strong exciton interactions between BChl 850 molecules in a circular symmetric arrangement, which lead to concentration of the oscillator strength in a few optically allowed transitions, corresponding to delocalized eigenstates. In BChl 850, a rapid red shift of the bleaching was observed. This relaxation process may be ascribed either to vibrational relaxation or exciton scattering. A similar red shift appears to occur in BChl 800.