Journal of Chemical Physics, Vol.100, No.7, 4820-4827, 1994
Spectral Diffusion and N-14 Quadrupole Splittings in Absorption Detected Magnetic-Resonance Hole-Burning Spectra of Photosynthetic Reaction Centers
Zero field absorption detected magnetic resonance hole burning measurements were performed on photosynthetic reaction centers of the bacteria Rhodobacter sphaeroides R26 and Rhodopseudomonas viridis. Extrapolation to zero microwave power yielded pseudohomogeneous linewidths of 2.0 MHz for Rhodopseudomonas viridis, 1.0 and 0.9 MHz for the protonated forms of Rhodobacter sphaeroides R26 with and without monomer bacteriochlorophyll exchanged, and 0.25 MHz as an upper limit for fully deuterated reaction centers of Rhodobacter sphaeroides R26. The measured linewidths were interpreted as being due to unresolved hyperfine interaction between the nuclear spins and the triplet electron spin, the line shape being determined by spectral diffusion among the nuclei. The difference in linewidths between Rhodobacter sphaeroides R26 and Rhodopseudomonas viridis is then explained by triplet delocalization on the special pair in the former, and localization on one dimer half on the latter. In the fully deuterated sample, four quadrupole satellites were observed in the hole spectra arising from the eight N-14 nitrogens in the special pair. The quadrupole parameters seem to be very similar for all nitrogens and were determined to kappa=1.25+/-0.1 MHz and eta=0.9+/-0.1 MHz.
Keywords:BACTERIUM RHODOPSEUDOMONAS-VIRIDIS;RHODOBACTER-SPHAEROIDES R-26;PHOTOINDUCED TRIPLET-STATE;ELECTRON-SPIN-RESONANCE;PRIMARY DONOR;ZERO-FIELD;RHODOSPIRILLUM-RUBRUM;DIFFERENCE SPECTRA;FLUORESCENCE-ODMR;ENERGY-TRANSFER