Kim Chang Woo, Lee Weon-Gyu, Kim Inkoo, Rhee Young Min
Department of Chemistry , Korea Advanced Institute of Science and Technology (KAIST) , Daejeon 34141 , Korea.
Department of Chemistry , Sungkyunkwan University , Suwon 16419 , Korea.
J Phys Chem A. 2019 Feb 14;123(6):1186-1197. doi: 10.1021/acs.jpca.8b10977. Epub 2019 Jan 31.
We study excitation energy transfer (EET) in a model three-site system with a mixed-quantum classical dynamics method, by focusing on the effect of an underdamped vibration. We construct two types of models where the underdamped vibration mode is included either in the quantum subsystem or in the classical bath. We show that the two models yield practically equivalent results despite the different depictions of the vibration. In particular, both models consistently demonstrate accelerations of population relaxation induced by quasi-resonant vibration. This indicates that intricate features of EET dynamics that have been frequently ascribed to the quantal nature of vibrations, such as vibronic mixing, can be successfully reproduced by using physically equivalent but classically described bath modes. The mechanism behind the observed quantum-classical correspondence is proposed. We also systematically examine how the structure of the spectating continuum phonon modes affects the vibronic resonance and observe that phonon modes with different time scales influence the resonance in different manners.
我们采用混合量子经典动力学方法，在一个模型化的三位点系统中研究激发能量转移（EET），重点关注欠阻尼振动的影响。我们构建了两种类型的模型，其中欠阻尼振动模式要么包含在量子子系统中，要么包含在经典浴中。我们表明，尽管对振动的描述不同，但这两种模型产生的结果实际上是等效的。特别是，两种模型都一致地证明了准共振振动引起的布居弛豫加速。这表明，EET动力学中经常归因于振动量子性质的复杂特征，如电子振动混合，可以通过使用物理上等效但经典描述的浴模式成功再现。我们提出了观察到的量子 - 经典对应背后的机制。我们还系统地研究了旁观连续体声子模式的结构如何影响电子振动共振，并观察到具有不同时间尺度的声子模式以不同方式影响共振。
