Vibrational vs. electronic coherences in 2D spectrum of molecular systems

@article{Butkus2012VibrationalVE,
  title={Vibrational vs. electronic coherences in 2D spectrum of molecular systems},
  author={Vytautas Butkus and Donatas Zigmantas and Leonas Valkunas and Darius Abramavi{\vc}ius},
  journal={Chemical Physics Letters},
  year={2012},
  volume={545},
  pages={40-43}
}
Two-dimensional spectroscopy has recently revealed the oscillatory behavior of the excitation dynamics of molecular systems. However, in the majority of cases there is considerable debate over what is actually being observed: excitonic or vibrational wavepacket motion or evidence of quantum transport. In this letter we present a method for distinguishing between vibrational and excitonic wavepacket motion, based on the phase and amplitude relationships of oscillations of distinct peaks as… 
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References

SHOWING 1-10 OF 16 REFERENCES
Comparison of Electronic and Vibrational Coherence Measured by Two-Dimensional Electronic Spectroscopy
The short pulse durations and broad frequency spectra of femtosecond laser pulses allow coherent superpositions of states to be prepared and probed. Two-dimensional electronic spectroscopy (2D ES)…
Vibrational wave packet induced oscillations in two-dimensional electronic spectra. I. Experiments
This is the first in a series of two papers investigating the effect of electron-phonon coupling in two-dimensional Fourier transformed electronic spectroscopy. We present a series of one- and…
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.
Coherent Intrachain Energy Migration in a Conjugated Polymer at Room Temperature
TLDR
An ultrafast polarization experiment specifically designed to observe quantum coherent dynamics in the intermediate coupling regime for electronic energy transfer suggests that quantum transport effects occur at room temperature when chemical donor-acceptor bonds help to correlate dephasing perturbations.
Manipulation of two-dimensional spectra of excitonically coupled molecules by narrow-bandwidth laser pulses
Complete expressions within the response function theory are derived for a coherent two-dimensional (2D) signal covering the finite-bandwidth and pulse-overlap effects. Ideal time domain, frequency…
Role of quantum coherence and environmental fluctuations in chromophoric energy transport.
TLDR
This work quantifies the biological importance of fundamental physical processes, such as the excitonic Hamiltonian evolution and phonon-induced decoherence, by their contribution to the efficiency of the primary photosynthetic event.
Many-body interactions in semiconductors probed by optical two-dimensional fourier transform spectroscopy.
TLDR
A two-dimensional spectrum correlates the phase (frequency) evolution of the nonlinear polarization field during the initial evolution and the final detection period and can identify couplings between resonances, separate quantum mechanical pathways, and distinguish among microscopic many-body interactions.
Extracting single and two-exciton couplings in photosynthetic complexes by coherent two-dimensional electronic spectra.
TLDR
It is demonstrated that by combining various two-dimensional optical signals it should be possible to invert spectroscopic data to reconstruct the full exciton Hamiltonian (energies and couplings).
Femtosecond Phase-Coherent Two-Dimensional Spectroscopy
TLDR
Femtosecond phase-coherent two-dimensional spectroscopy has been experimentally demonstrated as the direct optical analog of 2D nuclear magnetic resonance and the desired nonlinear polarization was selected by phase cycling.
Transport and correlated fluctuations in the nonlinear optical response of excitons
Closed expressions are derived for the femtosecond four-wave mixing of excitons which include slow Gaussian diagonal fluctuations (spectral diffusion) through the cumulant expansion and incoherent…
...
1
2
...