日本語
 
Help Privacy Policy ポリシー/免責事項
  詳細検索ブラウズ

アイテム詳細


公開

学術論文

Multi-faceted spectroscopic mapping of ultrafast nonadiabatic dynamics near conical intersections: A computational study

MPS-Authors
/persons/resource/persons257022

Chen,  Lipeng
Max Planck Institute for the Physics of Complex Systems, Max Planck Society;

External Resource
There are no locators available
Fulltext (restricted access)
There are currently no full texts shared for your IP range.
フルテキスト (公開)
公開されているフルテキストはありません
付随資料 (公開)
There is no public supplementary material available
引用

Sun, K., Xie, W., Chen, L., Domcke, W., & Gelin, M. F. (2020). Multi-faceted spectroscopic mapping of ultrafast nonadiabatic dynamics near conical intersections: A computational study. The Journal of Chemical Physics, 153(17):. doi:10.1063/5.0024148.


引用: https://hdl.handle.net/21.11116/0000-0007-F5E5-2
要旨
We studied spectroscopic signatures of the nonadiabatic dynamics at conical intersections formed by the lowest excited singlet states in pyrazine. We considered two ab initio models of conical intersections in the excited states of pyrazine developed by Sala et al. [Phys. Chem. Chem. Phys. 16, 15957 (2014)]: a two-state (B-2u and B-3u), five-mode model and a three-state (B-2u, B-3u, and A(u)), nine-mode model. We simulated the signals of three widely used techniques: time- and frequency-resolved fluorescence spectroscopy, transient absorption pump-probe spectroscopy, and electronic two-dimensional spectroscopy. The signals were calculated through third-order response functions, which, in turn, were evaluated with the numerically accurate multiple Davydov ansatz. We establish spectroscopic signatures of the optically dark A(u) state and demonstrate that the key features of the photoinduced dynamics, such as electronic/nuclear populations, electronic/nuclear coherences, and electronic/nuclear energy transfer processes, are imprinted in the spectroscopic signals. We show that a fairly complete picture of the nonadiabatic dynamics at conical intersections can be obtained when several spectroscopic techniques are combined. Provided that the time resolution is sufficient, time- and frequency-resolved fluorescence may provide the best visualization of the nonadiabatic dynamics near conical intersections.