Ab initio molecular orbital calculations of electronic couplings in the LH2 bacterial light-harvesting complex of Rps-acidophila

被引:172
作者
Scholes, GD
Gould, IR
Cogdell, RJ
Fleming, GR [1 ]
机构
[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA
[2] Univ Calif Berkeley, Lawrence Berkeley Lab, Phys Biosci Div, Berkeley, CA 94720 USA
关键词
D O I
10.1021/jp9839753
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The results of ab initio molecular orbital calculations of excited states and electronic couplings (for energy transfer) between the B800 and B850 bacteriochlorophyll a (Bchl) chromophores in the peripheral light-harvesting complex (LH2) of the purple photosynthetic bacterium Rhodopseudomonas acidophila are reported. Electronic couplings are estimated from "supermolecule" calculations of Bchl dimers using the CI-singles methodology and 3-21G" or 6-31G" basis sets. A scheme for dissecting the coupling into contributions from the Coulombic coupling and the short-range coupling (i.e., dependent on interchromophore orbital overlap) is reported. B850 couplings are calculated to be [total (Coulombic + short)]: intrapolypeptide dimer 320 (265 + 55) cm(-1) and interpolypeptide dimer 255 (195 + 60) cm(-1) at the CIS/6-31G* level. These results differ significantly from those estimated using the point dipole approximation. The effect of including Mg ligands (His residues) and H-bonding residues (Trp and Tyr) is also investigated. The consequences for superradiance and energy transfer dynamics and mechanism are discussed.
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页码:2543 / 2553
页数:11
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