Abstract
We present a theoretical study of excitation dynamics in the chlorosome antenna complex of green photosynthetic bacteria based on a recently proposed model for the molecular assembly. Our model for the excitation energy transfer (EET) throughout the antenna combines a stochastic time propagation of the excitonic wave function with molecular dynamics simulations of the supramolecular structure and electronic structure calculations of the excited states. We characterized the optical properties of the chlorosome with absorption, circular dichroism and fluorescence polarization anisotropy decay spectra. The simulation results for the excitation dynamics reveal a detailed picture of the EET in the chlorosome. Coherent energy transfer is significant only for the first 50 fs after the initial excitation, and the wavelike motion of the exciton is completely damped at 100 fs. Characteristic time constants of incoherent energy transfer, subsequently, vary from 1 ps to several tens of ps. We assign the time scales of the EET to specific physical processes by comparing our results with the data obtained from time-resolved spectroscopy experiments.
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Acknowledgment
The authors would like to thank Prof. Huub J. M. de Groot for fruitful discussions and the donation of the syn-anti chlorosome configuration template. We further appreciate Stéphanie Valleau and Prof. Jeongho Kim for very useful discussions and Nicolas Sawaya for the calculations of the CD spectra. T.F. thanks John Parkhill for advice on the calculations of the anisotropy decay and Yoshio Okiyama for providing a module of the optimally weighted charges. T. F., J. H., and A. A.-G. acknowledge support from the Center for Excitonics, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science and Office of Basic Energy Sciences under award DE-SC0001088. J. C. B. acknowledges support from Welcome Trust UK. S. K. S. and A. A.-G. also acknowledge Defense Threat Reduction Agency grant HDTRA1-10-1-0046. Further, A. A.-G. is grateful for the support from Defense Advanced Research Projects Agency grant N66001-10-1-4063, Camille and Henry Dreyfus Foundation, and Alfred P. Sloan Foundation. A. A.-G. also acknowledges generous support from the Corning Foundation.
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Fujita, T., Huh, J., Saikin, S.K. et al. Theoretical characterization of excitation energy transfer in chlorosome light-harvesting antennae from green sulfur bacteria. Photosynth Res 120, 273–289 (2014). https://doi.org/10.1007/s11120-014-9978-7
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DOI: https://doi.org/10.1007/s11120-014-9978-7