title: Multichromophoric Förster resonance energy transfer from b800 to b850 in the light harvesting complex 2: evidence for subtle energetic optimization by purple bacteria.
abstract: This work provides a detailed account of the application of our multichromophoric Förster resonance energy transfer (MC-FRET) theory (Phys. Rev. Lett. 2004, 92, 218301) for the calculation of the energy transfer rate from the B800 unit to the B850 unit in the light harvesting complex 2 (LH2) of purple bacteria. The model Hamiltonian consists of the B800 unit represented by a single bacteriochlorophyll (BChl), the B850 unit represented by its entire set of BChls, the electronic coupling between the two units, and the bath terms representing all environmental degrees of freedom. The model parameters are determined, independent of the rate calculation, from the literature data and by a fitting to an ensemble line shape. Comparing our theoretical rate and a low-temperature experimental rate, we estimate the magnitude of the BChl-Qy transition dipole to be in the range of 6.5-7.5 D, assuming that the optical dielectric constant of the medium is in the range of 1.5-2. We examine how the bias of the average excitation energy of the B800-BChl relative to that of the B850-BChl affects the energy transfer time by calculating the transfer rates based on both our MC-FRET theory and the original FRET theory, varying the value of the bias. Within our model, we find that the value of bias 260 cm-1, which we determine from the fitting to an ensemble line shape, is very close to the value at which the ratio between MC-FRET and FRET rates is a maximum. This provides evidence that the bacterial system utilizes the quantum mechanical coherence among the multiple chromophores within the B850 in a constructive way so as to achieve efficient energy transfer from B800 to B850.
authors: Department of Chemistry and Biochemistry, Queens College of the City University of New York, 65-30 Kissena Boulevard, Flushing, New York 11367-1597, USA. Seogjoo.Jang@qc.cuny.edu
authors: Seogjoo
authors: S
authors: Jang
authors: Marshall D
authors: MD
authors: Newton
authors: Robert J
authors: RJ
authors: Silbey
mesh_terms: D001426:Bacterial Proteins / Q000737:chemistry* / Q000378:metabolism; D001429:Bacteriochlorophylls / Q000737:chemistry* / Q000378:metabolism; D004735:Energy Transfer; D031541:Fluorescence Resonance Energy Transfer / Q000379:methods; D045342:Light-Harvesting Protein Complexes / Q000737:chemistry* / Q000378:metabolism; D008956:Models, Chemical; D020560:Proteobacteria / Q000737:chemistry* / Q000378:metabolism
chemical_list: C081521:B800-850 light-harvesting complex, bacteria; D001426:Bacterial Proteins; D001429:Bacteriochlorophylls; D045342:Light-Harvesting Protein Complexes