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Ultrafast Energy Transfer in Excitonically Coupled Molecules Induced by a Nonlocal Peierls Phonon

authors
H.-G. Duan, P. Nalbach, R. J. D. Miller, M. Thorwart
date published
Feb. 15, 2019
journal
The Journal of Physical Chemistry Letters
volume, number
6 (10)
pages
1206-1211
web page
https://pubs.acs.org/doi/10.1021/acs.jpclett.9b00242
doi
https://doi.org/10.1021/acs.jpclett.9b00242
abstract

Molecular vibration can influence exciton transfer via either a local (intramolecular) Holstein or a nonlocal (intermolecular) Peierls mode. We show that a strong vibronic coupling to a nonlocal mode dramatically speeds up the transfer by opening an additional transfer channel. This Peierls channel is rooted in the formation of a conical intersection of the excitonic potential energy surfaces. For increasing Peierls coupling, the electronically coherent transfer for weak coupling turns into an incoherent transfer of a localized exciton through the intersection for strong coupling. The interpretation in terms of a conical intersection intuitively explains recent experiments of ultrafast energy transfer in photosynthetic and photovoltaic molecular systems.