title: Long-time quantum simulation of the primary charge separation in bacterial photosynthesis.
abstract: Accurate quantum mechanical simulations of the primary charge transfer in photosynthetic reaction centers are reported. The process is modeled by three coupled electronic states corresponding to the photoexcited chlorophyll special pair (donor), the reduced bacteriopheophytin (acceptor), and the reduced accessory chlorophyll (bridge) that interact with a dissipative medium of protein and solvent degrees of freedom. The time evolution of the excited special pair is followed over 17 ps by using a fully quantum mechanical path integral scheme. We find that a free energy of the reduced accessory chlorophyll state approximately equal to 400 cm(-1) lower than that of the excited special pair state yields state populations in agreement with experimental results on wild-type and modified reaction centers. For this energetic configuration electron transfer is a two-step process.
authors.affiliation: School of Chemical Sciences, University of Illinois, Urbana 61801, USA.
authors.forename: N
authors.initials: N
authors.lastname: Makri
authors.forename: E
authors.initials: E
authors.lastname: Sim
authors.forename: D E
authors.initials: DE
authors.lastname: Makarov
authors.forename: M
authors.initials: M
authors.lastname: Topaler
mesh_terms: D001429:Bacteriochlorophylls / Q000737:chemistry / Q000378:metabolism; D003198:Computer Simulation; D007700:Kinetics; D045342:Light-Harvesting Protein Complexes; D008433:Mathematics; D008958:Models, Molecular; D008962:Models, Theoretical; D010674:Pheophytins / Q000737:chemistry* / Q000378:metabolism; D010788:Photosynthesis; D045322:Photosynthetic Reaction Center Complex Proteins / Q000737:chemistry* / Q000378:metabolism; D011789:Quantum Theory; D012242:Rhodobacter sphaeroides / Q000378:metabolism; D013816:Thermodynamics; D013997:Time Factors
chemical_list: D001429:Bacteriochlorophylls; D045342:Light-Harvesting Protein Complexes; D010674:Pheophytins; D045322:Photosynthetic Reaction Center Complex Proteins; C006678:bacteriopheophytin