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Multi-faceted spectroscopic mapping of ultrafast nonadiabatic dynamics near conical intersections: A computational study
Ist Teil von
The Journal of chemical physics, 2020-11, Vol.153 (17), p.174111-174111
Ort / Verlag
Melville: American Institute of Physics
Erscheinungsjahr
2020
Link zum Volltext
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Scitation
Beschreibungen/Notizen
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 (B2u and B3u), five-mode model and a three-state (B2u, B3u, and Au), 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 Au 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.