The role of resonant nuclear modes in vibrationally assisted energy transport: The LHCII complex.

@article{Bhattacharyya2020TheRO,
  title={The role of resonant nuclear modes in vibrationally assisted energy transport: The LHCII complex.},
  author={Pallavi Bhattacharyya and Graham R. Fleming},
  journal={The Journal of chemical physics},
  year={2020},
  volume={153 4},
  pages={
          044119
        }
}
In this paper, we discuss the explicit role of resonant nuclear/vibrational modes in mediating energy transport among chlorophylls in the Light-harvesting Complex II (LHCII), the major light-harvesting complex in green plants. The vibrational modes are considered to be resonant/quasi-resonant with the energy gap between electronic excitons. These resonant vibrations, along with the remaining nuclear degrees of freedom, constitute the environment/bath to the electronically excited system and… 
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References

SHOWING 1-10 OF 35 REFERENCES
Vibronic mixing enables ultrafast energy flow in light-harvesting complex II
TLDR
The involvement of the nuclear DoF during EET through the participation of higher-lying vibronic chlorophyll states is shown and observed oscillatory features are assigned to specific EET pathways, demonstrating a significant step in mapping evolution from energy to physical space.
Coherent Exciton Dynamics in the Presence of Underdamped Vibrations.
TLDR
Using a model dimer system, the frequency of the underdamped vibration is shown to have a strong effect on the exciton dynamics such that quantum coherent oscillations in the system can be present even in the case of strong noise.
Observation of Electronic Excitation Transfer Through Light Harvesting Complex II Using Two-Dimensional Electronic-Vibrational Spectroscopy.
TLDR
Two-dimensional electronic-vibrational spectra of LHCII isolated from spinach are presented, demonstrating the possibility of using this technique to track the transfer of electronic excitation energy between specific pigments within the complex.
Vibronic enhancement of exciton sizes and energy transport in photosynthetic complexes.
TLDR
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.
Enhancement of Vibronic and Ground-State Vibrational Coherences in 2D Spectra of Photosynthetic Complexes
TLDR
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.
Elucidation of near-resonance vibronic coherence lifetimes by nonadiabatic electronic-vibrational state character mixing
TLDR
A character change in the vibronic states is reported—reflective of property mixing between the electronic and vibrational states—induced by an interplay between system coupling parameters within the exciton-vibrational near-resonance regime.
Evidence for wavelike energy transfer through quantum coherence in photosynthetic systems
TLDR
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.
Spectroscopic elucidation of uncoupled transition energies in the major photosynthetic light-harvesting complex, LHCII
TLDR
In an investigation of the major light-harvesting complex of photosystem II (LHCII), a method based on polarized 2D electronic spectroscopy is developed to experimentally access the energies of the S0–S1 transitions in the chromophore site basis and shows that rotating the linear polarization of the incident laser pulses reveals previously hidden off-diagonal features.
Impact of environmentally induced fluctuations on quantum mechanically mixed electronic and vibrational pigment states in photosynthetic energy transfer and 2D electronic spectra.
TLDR
It is found that, at cryogenic temperatures, the electronic-vibrational quantum mixtures are rather robust, even under the influence of the fluctuations and despite the small Huang-Rhys factors of the Franck-Condon active vibrational modes, which results in long-lasting beating behavior of vibrational origin in the 2D electronic spectra.
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