Electronic excitation dynamics in multichromophoric systems described via a polaron-representation master equation
Electronic excitation dynamics in multichromophoric systems described via a polaron-representation master equation
复制标题
DOI：
10.1063/1.3652227
复制
发表时间：
2011-10-21
影响因子：
4.4
通讯作者：
Olaya-Castro, Alexandra
中科院分区：
文献类型：
--
作者：
Kolli, Avinash;Nazir, Ahsan;Olaya-Castro, Alexandra
我们推导了非马尔可夫时间无卷积极化子主方程的多位点版本[Jang，J. Chem Phys.129，101104（2008）]，以描述多色系统中的电子激发动力学。通过在组合框架（极化子框架）中处理电子和振动自由度，该理论能够在弱激子-声子耦合和强激子-声子耦合之间进行插值，并且能够解释初始非平衡浴态和空间相关环境。除了概述了在原始帧中观察到的任何电子系统的期望值的一般表达式，我们还讨论了马尔可夫近似和世俗近似的影响，强调它们不需要在未变换的帧中，尽管严格满足极化子帧。作为一个例子，使用四个站点子系统的芬娜-马修斯-奥尔森捕光复合物的理论的关键特征进行说明。对于包括局部模式的谱密度，我们表明，只有当考虑到非平衡浴效应时，才能观察到站点种群的振荡。此外，我们说明了这种形式主义如何使我们能够识别电子和振动成分的振荡动力学。(C)2011年美国物理学会。[doi：10.1063/1.3652227]
We derive a many-site version of the non-Markovian time-convolutionless polaron master equation [Jang , J. Chem Phys. 129, 101104 (2008)] to describe electronic excitation dynamics in multichromophoric systems. By treating electronic and vibrational degrees of freedom in a combined frame (polaron frame), this theory is capable of interpolating between weak and strong exciton-phonon coupling and is able to account for initial non-equilibrium bath states and spatially correlated environments. Besides outlining a general expression for the expected value of any electronic system observable in the original frame, we also discuss implications of the Markovian and Secular approximations highlighting that they need not hold in the untransformed frame despite being strictly satisfied in the polaron frame. The key features of the theory are illustrated using as an example a four-site subsystem of the Fenna-Mathews-Olson light-harvesting complex. For a spectral density including a localised mode, we show that oscillations of site populations may only be observed when non-equilibrium bath effects are taken into account. Furthermore, we illustrate how this formalism allows us to identify the electronic and vibrational components of the oscillatory dynamics. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3652227]