Jang Seogjoo, Hoyer Stephan, Fleming Graham, Whaley K Birgitta
Department of Chemistry and Biochemistry, Queens College and the Graduate Center, City University of New York, 65-30 Kissena Boulevard, Flushing, New York 11367, USA.
Department of Physics, University of California, Berkeley, California 94720, USA.
Phys Rev Lett. 2014 Oct 31;113(18):188102. doi: 10.1103/PhysRevLett.113.188102.
A generalized master equation (GME) governing quantum evolution of modular exciton density (MED) is derived for large scale light harvesting systems composed of weakly interacting modules of multiple chromophores. The GME-MED offers a practical framework to incorporate real time coherent quantum dynamics calculations of small length scales into dynamics over large length scales, and also provides a non-Markovian generalization and rigorous derivation of the Pauli master equation employing multichromophoric Förster resonance energy transfer rates. A test of the GME-MED for four sites of the Fenna-Matthews-Olson complex demonstrates how coherent dynamics of excitonic populations over coupled chromophores can be accurately described by transitions between subgroups (modules) of delocalized excitons. Application of the GME-MED to the exciton dynamics between a pair of light harvesting complexes in purple bacteria demonstrates its promise as a computationally efficient tool to investigate large scale exciton dynamics in complex environments.
针对由多个发色团的弱相互作用模块组成的大规模光捕获系统，推导了一个用于模块化激子密度（MED）量子演化的广义主方程（GME）。GME-MED提供了一个实用框架，可将小长度尺度的实时相干量子动力学计算纳入大长度尺度的动力学中，并且还提供了使用多发色团Förster共振能量转移速率对泡利主方程的非马尔可夫推广和严格推导。对Fenna-Matthews-Olson复合物的四个位点进行的GME-MED测试表明，离域激子的亚组（模块）之间的跃迁如何能够准确描述耦合发色团上激子种群的相干动力学。将GME-MED应用于紫色细菌中一对光捕获复合物之间的激子动力学，证明了其作为研究复杂环境中大规模激子动力学的计算高效工具的前景。
