English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT

Released

Journal Article

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
No external resources are shared
Fulltext (public)
There are no public fulltexts stored in PuRe
Supplementary Material (public)
There is no public supplementary material available
Citation

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): 174111. doi:10.1063/5.0024148.


Cite as: http://hdl.handle.net/21.11116/0000-0007-F5E5-2
Abstract
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.