Vibrational and Nonadiabatic Coherence in 2D Electronic Spectroscopy, the Jahn-Teller Effect, and Energy Transfer

Femtosecond two-dimensional (2D) Fourier transform spectroscopy generates and probes several types of coherence that characterize the couplings between vibrational and electronic motions. These couplings have been studied in molecules with Jahn-Teller conical intersections, pseudo-Jahn-Teller funnel...

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Bibliographic Details
Published in:Annual review of physical chemistry 2018-04, Vol.69 (1), p.327-352
Main Author: Jonas, David M
Format: Article
Language:English
Subjects:
2D oscillation maps
Bibliographic coupling
Coherence
correlated vibrations
Coupling (molecular)
Couplings
Dimers
Electron states
electronic coherence
Energy transfer
excitons
femtosecond Raman scattering
Fourier transforms
Funnels
Heat transfer
Intersections
Jahn-Teller effect
Molecular chains
Photosynthesis
quantum beats
resonance
Spectroscopy
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Summary:Femtosecond two-dimensional (2D) Fourier transform spectroscopy generates and probes several types of coherence that characterize the couplings between vibrational and electronic motions. These couplings have been studied in molecules with Jahn-Teller conical intersections, pseudo-Jahn-Teller funnels, dimers, molecular aggregates, photosynthetic light harvesting complexes, and photosynthetic reaction centers. All have closely related Hamiltonians and at least two types of vibrations, including one that is decoupled from the electronic dynamics and one that is nonadiabatically coupled. Polarized pulse sequences can often be used to distinguish these types of vibrations. Electronic coherences are rapidly obscured by inhomogeneous dephasing. The longest-lived coherences in these systems arise from delocalized vibrations on the ground electronic state that are enhanced by a nonadiabatic Raman excitation process. These characterize the initial excited-state dynamics. 2D oscillation maps are beginning to isolate the medium lifetime vibronic coherences that report on subsequent stages of the excited-state dynamics.
ISSN:0066-426X
1545-1593
DOI:10.1146/annurev-physchem-052516-050602