Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui 230026, China.
J Chem Phys. 2022 Aug 28;157(8):084119. doi: 10.1063/5.0104641.
Excitation energy transfer (EET) and electron transfer (ET) are crucially involved in photosynthetic processes. In reality, the photosynthetic reaction center constitutes an open quantum system of EET and ET, which manifests interplay of pigments, solar light, and phonon baths. So far, theoretical studies have been mainly based on master equation approaches in the Markovian condition. The non-Markovian environmental effect, which may play a crucial role, has not been sufficiently considered. In this work, we propose a mixed dynamic approach to investigate this open system. The influence of phonon bath is treated via the exact dissipaton equation of motion (DEOM), while that of photon bath is via the Lindblad master equation. Specifically, we explore the effect of non-Markovian quantum phonon bath on the coherent transfer dynamics and its manipulation on the current-voltage behavior. Distinguished from the results of the completely Markovian-Lindblad equation and those adopting the classical environment description, the mixed DEOM-Lindblad simulations exhibit transfer coherence up to a few hundred femtoseconds and the related environmental manipulation effect on the current. These non-Markovian quantum coherent effects may be extended to more complex and realistic systems and be helpful in the design of organic photovoltaic devices.
激发能量转移 (EET) 和电子转移 (ET) 在光合作用过程中至关重要。实际上，光合作用反应中心构成了 EET 和 ET 的开放量子系统，表现出色素、太阳光和声子浴之间的相互作用。到目前为止，理论研究主要基于马尔可夫条件下的主方程方法。而尚未充分考虑可能起关键作用的非马尔可夫环境效应。在这项工作中，我们提出了一种混合动力学方法来研究这个开放系统。声子浴的影响通过精确的耗散运动方程 (DEOM) 来处理，而光子浴的影响则通过林德布拉德主方程来处理。具体来说，我们探索了非马尔可夫量子声子浴对相干转移动力学的影响及其对电流-电压行为的操控。与完全马尔可夫-林德布拉德方程的结果以及采用经典环境描述的结果不同，混合的 DEOM-林德布拉德模拟表现出长达几百飞秒的转移相干性，以及环境对电流的相关操控效应。这些非马尔可夫量子相干效应可以扩展到更复杂和现实的系统，并有助于有机光伏器件的设计。
