Vibronic coupling in energy transfer dynamics and two-dimensional electronic-vibrational spectra
Vibronic coupling in energy transfer dynamics and two-dimensional electronic-vibrational spectra
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DOI：
10.1063/5.0056477
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发表时间：
2021-08-07
影响因子：
4.4
通讯作者：
Fleming, Graham R.
中科院分区：
文献类型：
--
作者：
Arsenault, Eric A.;Schile, Addison J.;Fleming, Graham R.
我们引入了一个异二聚体模型，在该模型中，可以明确地研究电子振动耦合的多种机制及其对能量转移的影响。我们认为振动耦合，通过任一弗兰克-康登活动中的每个网站在异源二聚体有一个本地的电子-声子耦合或赫兹伯格-泰勒活动中的跃迁偶极矩耦合的网站有一个明确的振动模式依赖性。我们已经计算了这个模型的二维电子振动（2DEV）光谱，同时改变这两种效应的大小，发现2DEV光谱包含静态和动态签名的两种类型的电子振动耦合。Franck-Condon活动通过观察到的激子结构的变化而出现，而Herzberg-Teller活动在模仿较低能量激子结构的显着边带跃迁的出现中是明显的。从模拟的2DEV光谱分析得到的量子拍模式的比较表明，这种技术可以报告的能量转移的机制，阐明了实验确定的特定的振动耦合机制在这样的过程中的作用的手段。
We introduce a heterodimer model in which multiple mechanisms of vibronic coupling and their impact on energy transfer can be explicitly studied. We consider vibronic coupling that arises through either Franck-Condon activity in which each site in the heterodimer has a local electron-phonon coupling or Herzberg-Teller activity in which the transition dipole moment coupling the sites has an explicit vibrational mode-dependence. We have computed two-dimensional electronic-vibrational (2DEV) spectra for this model while varying the magnitude of these two effects and find that 2DEV spectra contain static and dynamic signatures of both types of vibronic coupling. Franck-Condon activity emerges through a change in the observed excitonic structure, while Herzberg-Teller activity is evident in the appearance of significant side-band transitions that mimic the lower-energy excitonic structure. A comparison of quantum beating patterns obtained from analysis of the simulated 2DEV spectra shows that this technique can report on the mechanism of energy transfer, elucidating a means of experimentally determining the role of specific vibronic coupling mechanisms in such processes.