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… 
Influences of quantum mechanically mixed electronic and vibrational pigment states in 2D electronic spectra of photosynthetic systems: Strong electronic coupling cases
In 2D electronic spectroscopy studies, long-lived quantum beats have recently been observed in photosynthetic systems, and it has been suggested that the beats are produced by quantum mechanically
Influence of weak vibrational-electronic couplings on 2D electronic spectra and inter-site coherence in weakly coupled photosynthetic complexes.
TLDR
This work calculates the correlation between optical pump interactions and subsequent entanglement between sites, as measured by the concurrence, and compares the calculated 2D spectra with the site-probe response, and shows that an on-resonance vibration with Huang-Rhys factor as small as S = 0.005 and the most strongly coupled off-Resonance vibrations give rise to long-lived, purely vibrational coherences at 77 K.
Signatures of vibronic coupling in two-dimensional electronic-vibrational and vibrational-electronic spectroscopies.
TLDR
A system Hamiltonian is developed here to lay a foundation for interpreting the 2D EV and 2D VE signals that arise from a vibronically coupled molecular system in the condensed phase and explores how these vibronic interactions are manifested in the positions, amplitudes, and line shapes of the peaks in 2D EVs and VE spectroscopies.
Vibronic coupling in energy transfer dynamics and two-dimensional electronic-vibrational spectra.
TLDR
A comparison of quantum beating patterns obtained from analysis of the simulated 2DEV spectra shows that this technique can report on the mechanism of energy transfer, elucidating a means of experimentally determining the role of specific vibronic coupling mechanisms in such processes.
A method for the direct measurement of electronic site populations in a molecular aggregate using two-dimensional electronic-vibrational spectroscopy.
TLDR
This work derives response functions for the 2DEV spectrum of a molecular dimer and proposes a method by which 2DEV spectra could be used to directly measure the electronic site populations as a function of time following the initial electronic excitation.
Two-Dimensional Electronic-Vibrational Spectroscopy of Coupled Molecular Complexes: A Near-Analytical Approach.
TLDR
Although the interpretation of 2DEV spectra is considerably more complex than that for weakly coupled systems, the richness of the spectra and the necessity to consider both visible and infrared transition moments suggest that such analysis will be very valuable in characterizing the role of vibronic effects in ultrafast molecular dynamics.
Electronic energy transfer through non-adiabatic vibrational-electronic resonance. I. Theory for a dimer.
TLDR
A generalized dimer model incorporates asymmetries between pigments, coupling to the environment, and the doubly excited state relevant for nonlinear spectroscopy, and shows that anti-correlated vibrations increase the range and speed of vibronically resonant energy transfer.
Theoretical study of excitation energy transfer and nonlinear spectroscopy of photosynthetic light‐harvesting complexes using the nonperturbative reduced dynamics method
The highly efficient excitation energy transfer (EET) processes in photosynthetic light‐harvesting complexes have attracted much recent research interests. Experimentally, spectroscopic studies have
Effects of Different Quantum Coherence on the Pump-Probe Polarization Anisotropy of Photosynthetic Light-Harvesting Complexes: A Computational Study.
TLDR
Three model dimer systems with different prespecified quantum coherence are simulated, and the results show that their different spectral characteristics can be used to determine the type of coherence during the spectral process.
Vibronic resonance is inadequately described by one-particle basis sets.
TLDR
It is shown that several features such as vibronic exciton delocalization and vibrational distortions associated with electronic excitations, which ultimately dictate the excited state wavepacket motions and relaxation processes, are fundamentally not described by basis sets that restrict ground state vibrations.
...
1
2
3
4
5
...

References

SHOWING 1-10 OF 137 REFERENCES
Origin of long-lived oscillations in 2D-spectra of a quantum vibronic model: electronic versus vibrational coherence.
TLDR
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
TLDR
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.
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.
Non-classicality of the molecular vibrations assisting exciton energy transfer at room temperature
TLDR
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.
TLDR
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
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.
Microscopic quantum coherence in a photosynthetic-light-harvesting antenna
TLDR
A fluorescence-detected single-molecule experiment with phase-locked excitation pulses is proposed to investigate the coherent dynamics at the level of a single molecule without hindrance by ensemble averaging and indicates that the decay of the observed quantum coherence can be understood as ensemble dephasing.
High frequency vibrational modulations in two-dimensional electronic spectra and their resemblance to electronic coherence signatures.
TLDR
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
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.
...
1
2
3
4
5
...