How do vibrations, resonant with excitonic energy gap, affect the dynamics of EET?

IR modes, that are resonant with the energy gap between a pair of excitons, could significantly affect the dynamics of electronic energy transport in light-harvesting complexes, possibly resulting in long-lived coherences and faster population relaxation [1-3]. This resonance leads to the formation of mixed vibronic states that are seen to have a strong presence in the theoretically evaluated 2DEV (Two Dimensional Electronic Vibrational) spectra [4]. We are seeking to obtain a stronger mechanistic understanding of the energy transport and how 2DEV spectroscopy could be used to investigate this.

Helpful Background Reading:

  1. The role of non-equilibrium vibrational structures in electronic coherence and recoherence in pigment − protein complexes. A.W. Chin, J. Prior, R. Rosenbach, F. Caycedo-Soler, S.F. Huelga, and M.B. Plenio, Nat. Phys., 9, 113 (2013).

  2. Mechanistic Regimes of Vibronic Transport in a Heterodimer and the Design Principle of Incoherent Vibronic Transport in Phycobiliproteins. D.I.G. Bennett, P. Maly, C. Kreisbeck, R. van Grondelle, and A. Aspuru-Guzik, J. Phys. Chem. Lett., 9, 2665 −2670 (2018).

  3. Elucidation of near-Resonance Vibronic Coherence Lifetimes by Nonadiabatic Electronic-Vibrational State Character Mixing. S-H. Yeh, R.D. Hoehn, M.A. Allodi, G.S. Engel, S. Kais, Proc. Natl. Acad. Sci. USA, 201701390 (2018).

  4. Two-Dimensional Electronic Vibrational Spectroscopy of Coupled Molecular Complexes: A Near-Analytical Approach. P. Bhattacharyya, and G.R. Fleming, J. Phys. Chem. Lett., 10, 2081-2089 (2019).