Phase-space wavepacket dynamics of internal conversion via conical intersection: Multi-state quantum Fokker-Planck equation approach

We theoretically investigate internal conversion processes of a photoexcited molecule in a condensed phase. The molecular system is described by two-dimensional adiabatic ground and excited potential energy surfaces that are coupled to heat baths. We quantify the role of conical intersection (CI) an...

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Bibliographic Details
Published in:Chemical physics 2018-11, Vol.515, p.203-213
Main Authors: Ikeda, Tatsushi, Tanimura, Yoshitaka
Format: Article
Language:English
Subjects:
Avoided crossing
Condensed phase
Conical intersection
Internal conversion
Multi-state quantum Fokker-Planck equation
Non-adiabatic transition
Wavepacket dynamics
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Summary:We theoretically investigate internal conversion processes of a photoexcited molecule in a condensed phase. The molecular system is described by two-dimensional adiabatic ground and excited potential energy surfaces that are coupled to heat baths. We quantify the role of conical intersection (CI) and avoided crossing (AC) in the PESs in dissipative environments by simulating the time evolution of wavepackets to compute the lifetime of the excited wavepacket, yield of the product, and adiabatic electronic coherence. For this purpose, we employ the multi-state quantum Fokker-Planck equation (MSQFPE) for a two-dimensional Wigner space utilizing the Wigner–Moyal expansion for the potential term and the Brinkman hierarchy expression for the momentum. We find that the calculated results are significantly different between the CI and AC cases due to the transition in the tuning mode and vibrational motion in the coupling mode.
ISSN:0301-0104
DOI:10.1016/j.chemphys.2018.07.013