Department of Chemistry and Center for Quantum Science and Engineering, National Taiwan University, Taipei City 106, Taiwan.
Department of Physics and Institute of Modern Physics, Ningbo University, Ningbo 315211, China.
J Chem Phys. 2013 Dec 14;139(22):224112. doi: 10.1063/1.4840795.
The small polaron quantum master equation (SPQME) proposed by Jang et al. [J. Chem. Phys. 129, 101104 (2008)] is a promising approach to describe coherent excitation energy transfer dynamics in complex molecular systems. To determine the applicable regime of the SPQME approach, we perform a comprehensive investigation of its accuracy by comparing its simulated population dynamics with numerically exact quasi-adiabatic path integral calculations. We demonstrate that the SPQME method yields accurate dynamics in a wide parameter range. Furthermore, our results show that the accuracy of polaron theory depends strongly upon the degree of exciton delocalization and timescale of polaron formation. Finally, we propose a simple criterion to assess the applicability of the SPQME theory that ensures the reliability of practical simulations of energy transfer dynamics with SPQME in light-harvesting systems.
张等人提出的小极化子量子主方程（SPQME）[J. Chem. Phys. 129, 101104 (2008)]是描述复杂分子体系中相干激发能量转移动力学的一种很有前途的方法。为了确定 SPQME 方法的适用范围，我们通过将其模拟的群体动力学与数值精确的准绝热路径积分计算进行比较，对其准确性进行了全面研究。我们证明了 SPQME 方法在很宽的参数范围内可以产生准确的动力学。此外，我们的结果表明，极化子理论的准确性强烈依赖于激子离域的程度和极化子形成的时间尺度。最后，我们提出了一个简单的准则来评估 SPQME 理论的适用性，该准则确保了在光收集系统中使用 SPQME 对能量转移动力学进行实际模拟的可靠性。
