分子组装体中的强激子-振动耦合。HEOM空间中极化子变换的动力学
Strong Exciton-Vibrational Coupling in Molecular Assemblies. Dynamics using the Polaron Transformation in HEOM Space
摘要：
在Frenkel激子动力学的上下文中聚集分子的极化子变换技术有利于治疗的对角元素归因于电子激发态人口去耦与振动自由度的波动。在这篇文章中，我们第一次描述了如何极化子变换可以应用在“层次运动方程”（HEOM）技术的背景下治疗的开放量子系统的所有振动组件归因于一个环境。利用生成函数方法引入激发态势能面的位移，我们得到了类似于时间传播的极化子变换的分级方程。我们证明了所开发的方法的适用性，通过计算动力学的欠阻尼和过阻尼振荡器耦合到电子激发的单体没有和以前的极化子变换和研究的动力学的期望值的各自的振动坐标。此外，我们调查的动力学的二聚体的势垒可比的热能之间的最小值的较低的激子势能面。事实证明，本地化的假设在单体单元具有能量较高的潜在的最小值，通过极化子转换，有很大的影响的转移动力学。在这里，极化子变换是在局域基还是激子基上进行有明显的区别。这反映了这样一个事实，即极化子变换只占振动的平衡，而不是激子动力学。我们勾勒出一种方法来弥补这一缺点，鉴于获得一个初始状态的计算分子聚集体的发射光谱。
英文摘要：
In the context of Frenkel exciton dynamics in aggregated molecules the polaron transformation technique facilitates a treatment where diagonal elements attributed to electronic excited-state populations are decoupled from fluctuations associated with vibrational degrees-of-freedom. In this article we describe for the first time how the polaron transformation can be applied in the context of the "Hierarchical Equations of Motion" (HEOM) technique for treatment of open quantum systems with all vibrational components attributed to an environment. By using a generating function approach to introduce a shift in the excited state potential energy surface, we derive hierarchical equations for polaron transformation in analogy to those for time propagation. We demonstrate the applicability of the developed approach by calculating the dynamics of underdamped and overdamped oscillators coupled to electronic excitation of a monomer without and with previous polaron transformation and study the dynamics of the expectation value of the respective vibrational coordinates. Furthermore, we investigate the dynamics of a dimer with a barrier comparable to the thermal energy between the minima of the lower excitonic potential energy surface. It turns out that the assumption of localization at the monomer unit with energetically higher potential minimum, introduced via polaron transformation, has a substantial influence on the transfer dynamics. Here, it makes a clear difference whether the polaron transformation is performed in the local or exciton basis. This reflects the fact that the polaron transformation only accounts for equilibration of the vibrational, but not of the excitonic dynamics. We sketch an approach to compensate this shortcoming in view of obtaining an initial state for the calculation of emission spectra of molecular aggregates.
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