Leveraging Dynamical Symmetries in Two-Dimensional Electronic Spectra to Extract Population Transfer Pathways
Leveraging Dynamical Symmetries in Two-Dimensional Electronic Spectra to Extract Population Transfer Pathways
复制标题
利用二维电子光谱中的动态对称性来提取种群转移路径
DOI：
10.1021/acs.jpca.2c01993
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Engel, Gregory S.
中科院分区：
文献类型：
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作者：
Higgins, Jacob S.;Dardia, Anna R.;Ndife, Chidera J.;Lloyd, Lawson T.;Bain, Elizabeth M.;Engel, Gregory S.
我们提出了一种从二维电子光谱信号中确定分离种群转移动力学的方法。该分析的核心是描述激发态系统的所有可能的子系如何在种群时间内演化。当使用双面费曼路径（包括种群时间动力学）对这些动力学进行图解映射时，对角线和对角线以下交叉峰信号的激发态吸收和基态漂白恢复动力学之间出现了有用的对称性。这种对称性允许从光谱中去除路径，以隔离根据能量传递动力学演变的信号。我们描述了一种适合能量传递时间常数的回归过程，并利用模拟的二维光谱表征了该方法在各种复杂激发态系统中的准确性。我们的研究结果表明，该方法对于提取多态激子系统、包含影响信号动力学的暗态系统和具有干扰振动弛豫途径的系统中的超快能量转移具有鲁棒性。这个程序可以用来准确地提取能量转移动力学从各种各样的凝聚相系统。
We present a method to deterministically isolate population transfer kinetics from two-dimensional electronic spectroscopic signals. Central to this analysis is the characterization of how all possible subensembles of excited state systems evolve through the population time. When these dynamics are diagrammatically mapped by using double-sided Feynman pathways where population time dynamics are included, a useful symmetry emerges between excited state absorption and ground state bleach recovery dynamics of diagonal and below diagonal cross-peak signals. This symmetry allows removal of pathways from the spectra to isolate signals that evolve according to energy transfer kinetics. We describe a regression procedure to fit to energy transfer time constants and characterize the accuracy of the method in a variety of complex excited state systems using simulated two-dimensional spectra. Our results show that the method is robust for extracting ultrafast energy transfer in multistate excitonic systems, systems containing dark states that affect the signal kinetics, and systems with interfering vibrational relaxation pathways. This procedure can be used to accurately extract energy transfer kinetics from a wide variety of condensed phase systems.