Impact of environmentally induced fluctuations on quantum mechanically mixed electronic and vibrational pigment states in photosynthetic energy transfer and 2D electronic spectra.

@article{Fujihashi2015ImpactOE,
  title={Impact of environmentally induced fluctuations on quantum mechanically mixed electronic and vibrational pigment states in photosynthetic energy transfer and 2D electronic spectra.},
  author={Yuta Fujihashi and Graham R. Fleming and Akihito Ishizaki},
  journal={The Journal of chemical physics},
  year={2015},
  volume={142 21},
  pages={
          212403
        }
}
Recently, nuclear vibrational contribution signatures in two-dimensional (2D) electronic spectroscopy have attracted considerable interest, in particular as regards interpretation of the oscillatory transients observed in light-harvesting complexes. These transients have dephasing times that persist for much longer than theoretically predicted electronic coherence lifetime. As a plausible explanation for this long-lived spectral beating in 2D electronic spectra, quantum-mechanically mixed… 

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References

SHOWING 1-10 OF 133 REFERENCES

Origin of long-lived oscillations in 2D-spectra of a quantum vibronic model: electronic versus vibrational coherence.

These results link recently proposed microscopic, non-equilibrium mechanisms to support long lived coherence at ambient temperatures with actual experimental observations of oscillatory behaviour using 2D photon echo techniques to corroborate the fundamental importance of the interplay of electronic and vibrational degrees of freedom in the dynamics of light harvesting aggregates.

Two-dimensional spectroscopy of electronic couplings in photosynthesis

This work directly measures electronic couplings in a molecular complex, the Fenna–Matthews–Olson photosynthetic light-harvesting protein, and finds distinct energy transport pathways that depend sensitively on the detailed spatial properties of the delocalized excited-state wavefunctions of the whole pigment–protein complex.

Vibronic enhancement of exciton sizes and energy transport in photosynthetic complexes.

Investigation of the impact of vibronic couplings on the electronic structures and relaxation mechanisms of two cyanobacterial light-harvesting proteins suggests that the distinct behaviors of these closely related proteins are understood on the same footing only in a basis of joint electronic-nuclear states.

Non-classicality of the molecular vibrations assisting exciton energy transfer at room temperature

In prototype dimers present in a variety of photosynthetic antennae, efficient vibration-assisted energy transfer in the sub-picosecond timescale and at room temperature can manifest and benefit from non-classical fluctuations of collective pigment motions.

Two-dimensional spectroscopy of a molecular dimer unveils the effects of vibronic coupling on exciton coherences.

This work presents measurements and calculations on a solvated molecular homodimer with clearly resolvable oscillations in the corresponding two-dimensional spectra and finds that although calculations predict a prolongation of this coherence due to vibronic coupling, the combination of dynamic disorder and vibrational relaxation leads to a coherence decay on a timescale comparable to the electronic dephasing time.

Enhancement of Vibronic and Ground-State Vibrational Coherences in 2D Spectra of Photosynthetic Complexes

A vibronic-exciton model is applied to investigate the recently proposed mechanism of enhancement of coherent oscillations due to mixing of electronic and nuclear degrees of freedom and concludes that both type of coherences have a similar magnitude at longer population time.

High frequency vibrational modulations in two-dimensional electronic spectra and their resemblance to electronic coherence signatures.

The results show that these anticorrelated oscillations occur for vibrational wavepackets and not exclusively for electronic coherences as has been assumed previously.

Evidence for wavelike energy transfer through quantum coherence in photosynthetic systems

Previous two-dimensional electronic spectroscopy investigations of the FMO bacteriochlorophyll complex are extended, and direct evidence is obtained for remarkably long-lived electronic quantum coherence playing an important part in energy transfer processes within this system is obtained.

Origin of Long-Lived Coherences in Light-Harvesting Complexes

A vibronic exciton model is applied to explain the long-lived oscillatory features in the two-dimensional electronic spectra of the Fenna–Matthews–Olson (FMO) complex and predicts oscillations with dephasing times of 1.3 ps at 77 K, which is in a good agreement with the experimental results.
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