Vibrational control of electron-transfer reactions: a feasibility study for the fast coherent transfer regime.

@article{Antoniou2015VibrationalCO,
  title={Vibrational control of electron-transfer reactions: a feasibility study for the fast coherent transfer regime.},
  author={Panayiotis Antoniou and Zhe Ma and P. Zhang and David N. Beratan and Spiros S. Skourtis},
  journal={Physical chemistry chemical physics : PCCP},
  year={2015},
  volume={17 46},
  pages={
          30854-66
        }
}
Molecular vibrations and electron-vibrational interactions are central to the control of biomolecular electron and energy-transfer rates. The vibrational control of molecular electron-transfer reactions by infrared pulses may enable the precise probing of electronic-vibrational interactions and of their roles in determining electron-transfer mechanisms. This type of electron-transfer rate control is advantageous because it does not alter the electronic state of the molecular electron-transfer… 
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Vibrational control of molecular electron transfer reactions
ABSTRACT Vibrational motions promote molecular electron transfer (ET) reactions by bringing electron donor and electron acceptor electronic states to fleeting resonance, and by modulating the…
On the mechanism of vibrational control of light-induced charge transfer in donor-bridge-acceptor assemblies.
TLDR
The experiments reveal a complex combination of vibronic mechanisms responsible for the observed changes in electron transfer rates and pathways, and raise new fundamental questions about the function of vibrational processes immediately following charge transfer photoexcitation.
Directing the path of light-induced electron transfer at a molecular fork using vibrational excitation.
TLDR
It is shown that the pathway that is vibrationally perturbed during UV-induced electron transfer is dramatically slowed down compared to its unperturbed counterpart, delivering a new opportunity for precise perturbative control of electronic energy propagation in molecular devices.
Coherent control of long-range photoinduced electron transfer by stimulated X-ray Raman processes
TLDR
It is shown that X-ray pulses resonant with selected core transitions can manipulate electron transfer (ET) in molecules with ultrafast and atomic selectivity, and possible protocols for coherently controlling ET dynamics in donor–bridge–acceptor (DBA) systems are presented.
Electron Transfer Assisted by Vibronic Coupling from Multiple Modes.
TLDR
The DFT-MJL approach provides robust and accurate predictions of ET rates spanning over 4 orders of magnitude in the 106-1010 s-1 range, and provides insight into the interplay between vibrational degrees of freedom and changes in electronic state.
Identifying electron transfer coordinates in donor-bridge-acceptor systems using mode projection analysis
TLDR
An analysis of the vibrational modes that couple and drive the state-to-state electronic transfer branching ratios in a model donor-bridge-acceptor system consisting of a phenothiazine-based donor linked to a naphthalene-monoimide acceptor via a platinum-acetylide bridging unit suggests that IR excitation of the acetylene modes preferentially enhances charge-recombination transition relative to charge-separation.
Polariton Mediated Electron Transfer via Cavity Quantum Electrodynamics
We investigate the polariton-mediated electron transfer reaction in a model system with analytic rate constant theory and direct quantum dynamical simulations. We demonstrate that the photoinduced…
Ultrafast Electron Dynamics in Solar Energy Conversion.
TLDR
The light-induced electron processes underlying the function of several molecular and hybrid materials currently under development for solar energy applications in dye or quantum dot-sensitized solar cells, polymer-fullerene polymer solar cells," organometal halide perovskite solar cells", and finally some photocatalytic systems are discussed.
Quantum ergodicity and energy flow in molecules
We review a theory for coupled many-nonlinear oscillator systems that describes quantum ergodicity and energy flow in molecules. The theory exploits the isomorphism between quantum energy flow in…
How can infra-red excitation both accelerate and slow charge transfer in the same molecule?
A UV-IR-Vis 3-pulse study of infra-red induced changes to electron transfer (ET) rates in a donor–bridge–acceptor species finds that charge-separation rates are slowed, while charge-recombination…
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References

SHOWING 1-10 OF 80 REFERENCES
Toward control of electron transfer in donor-acceptor molecules by bond-specific infrared excitation
TLDR
It is demonstrated how the outcome of light-induced ET can be radically altered by mode-specific infrared (IR) excitation of vibrations that are coupled to the ET pathway, effectively switching a charge separation pathway off.
Contemporary Issues in Electron Transfer Research
This is an overview of some of the important, challenging, and problematic issues in contemporary electron transfer research. After a qualitative discussion of electron transfer, its time and…
Fluctuations in biological and bioinspired electron-transfer reactions.
TLDR
The critical timescales at play for ET reactions in fluctuating media are discussed, highlighting issues of the Condon approximation, average medium versus fluctuation-controlled electron tunneling, gated and solvent relaxation controlled electron transfer, and the influence of inelastic tunneling on electronic coupling pathway interferences.
Correlating the motion of electrons and nuclei with two-dimensional electronic–vibrational spectroscopy
TLDR
2D electronic–vibrational spectroscopy is developed, capable of correlating the electronic and vibrational degrees of freedom, and applied to the study of the 4-(di-cyanomethylene)-2-methyl-6-p-(dimethylamino)styryl-4H-pyran (DCM) laser dye in deuterated dimethyl sulfoxide and its excited state relaxation pathways.
Steering electrons on moving pathways.
TLDR
Recent studies are described that address puzzling questions of how conformational distributions, excited-state polarization, and electronic and nuclear dynamical effects influence ET in macromolecules, including the tunneling, resonant transport, and hopping regimes.
Vibrational energy transfer dynamics in ruthenium polypyridine transition metal complexes.
TLDR
The present study investigates vibrational energy transport in the ground and the electronic excited state of Ru(4,4'-(COOEt)2-2,2-bpy)2(NCS)2, a close relative of the efficient "N3" dye used in dye-sensitized solar cells and shows that it is dramatically faster in the latter.
Electron transfer through fluctuating bridges: On the validity of the superexchange mechanism and time-dependent tunneling matrix elements
The superexchange mechanism of electron-transfer reactions is studied for time-dependent donor–bridge–acceptor systems. It is shown that superexchange may not be a relevant mechanism in a situation…
Electron transfer : from isolated molecules to biomolecules
Electron Transfer Past and Future (R. Marcus). Electron Transfer Reactions in Solution: A Historical Perspective (N. Sutin). Electron Transfer--From Isolated Molecules to Biomolecules (M. Bixon & J.…
Probing and Exploiting the Interplay between Nuclear and Electronic Motion in Charge Transfer Processes.
TLDR
The experiments show that intramolecular vibrational redistribution and vibrational energy transfer are up to an order of magnitude faster in the triplet charge transfer excited state than in the ground state and suggest that one may perturb electronic movement by stimulating structural motion along the reaction coordinate using IR light.
Protein dynamics and electron transfer: electronic decoherence and non-Condon effects.
TLDR
The autocorrelation function of the donor-acceptor tunneling matrix element for six Ru-azurin derivatives is computed and it is shown that for azurin, the correlation function is remarkably insensitive to tunneling pathway structure.
...
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