Solvent Effects in Nonadiabatic Electron‐Transfer Reactions: Theoretical Aspects

Barzykin, A. V.; Frantsuzov, Pavel A.; Seki, Kazuhiko; Tachiya, M.

doi:10.1002/0471231509.ch9

Cited by 120 publications

(142 citation statements)

References 122 publications

(225 reference statements)

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“…There is however no consistent information on its value. Although DACs with V el close to 1 eV most certainly exist, the model used here is only applicable for nonadiabatic reactions with a rather small V el , i.e., V el Ͻk B T. 57 Therefore, the investigation of the spectral effect is limited to this range of V el . For substantially larger V el , the adiabatic theory of electronic transitions has to be applied.…”

Section: Numerical Results and Discussionmentioning

confidence: 99%

Effect of the excitation pulse carrier frequency on the ultrafast charge recombination dynamics of donor-acceptor complexes: Stochastic simulations and experiments

Федунов

Feskov

Ivanov

et al. 2004

The Journal of Chemical Physics

111

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The influence of the excitation pulse carrier frequency on the ultrafast charge recombination dynamics of excited donor-acceptor complexes has been explored both theoretically and experimentally. The theoretical description involves the explicit treatment of both the optical formation of the nuclear wave packet on the excited free energy surface and its ensuing dynamics. The wave packet motion and the electronic transition are described within the framework of the stochastic point-transition approach. It is shown that the variation of the pulse carrier frequency within the absorption band can significantly change the effective charge recombination dynamics. The mechanism of this phenomenon is analyzed and a semiquantitative interpretation is suggested. The role of the vibrational coherence in the recombination dynamics is discussed. An experimental investigation of the ultrafast charge recombination dynamics of two donor-acceptor complexes in valeronitrile also is presented. The decays of the excited state population were found to be highly nonexponential, the degree of non-exponentiality depending on the excitation frequency. For one complex, the charge recombination dynamics was found to slow down upon increasing the excitation frequency, while the opposite behavior was observed with the other complex. These experimental observations follow qualitatively the predictions of the simulations.

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Section: Numerical Results and Discussionmentioning

confidence: 99%

Effect of the excitation pulse carrier frequency on the ultrafast charge recombination dynamics of donor-acceptor complexes: Stochastic simulations and experiments

Федунов

Feskov

Ivanov

et al. 2004

The Journal of Chemical Physics

111

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“…[12,13,23,24] This is necessary because the fast transients can only be rationalized by fast initial electron-transfer rates, for which both effects become relevant. The same electron-transfer model has also been used in our analysis of the RW experiment; the model is shown in Equation (1) and the Levich-Dogonadze pre-exponential term is given by Equation (2).…”

Section: Theoretical Description and Approximationsmentioning

confidence: 99%

On the Coherent Description of Diffusion‐Influenced Fluorescence Quenching Experiments II: Early Events

Angulo¹,

Kattnig²,

Rosspeintner³

et al. 2010

Chemistry A European J

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In a previous article we showed how to perform and analyze steady-state and nanosecond time-resolved experiments on fluorescence quenching by electron transfer in a coherent manner. Now, by making use of a superior time resolution, we explore the first stages of this kind of reaction. The novel information gained enables us to merge the results on the viscosity and the driving-force dependencies of the reaction rate. A unique set of parameters for a single reaction channel suffices to describe all the results in the frame of differential encounter theory for diffusion-influenced, bimolecular, remote electron-transfer reactions. The inclusion of the solvent structure is crucial for the understanding of the reaction kinetics. To the authors' best knowledge, this is the first time that such a comprehensive set of data has been successfully and jointly explained in the field, with physically sound parameters for electron-transfer reactions.

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“…3 For ET, this regime corresponds to solvent-controlled reactions when the preexponential factor of the rate is inversely proportional to a solvent relaxation time. 4 One can anticipate the next step in this hierarchy of relaxation times when the time of the reaction itself (not just the time of barrier passage) becomes comparable to the solvent relaxation time. Such conditions, which apply to ultrafast reactions in high-temperature solvents and to reactions in slowly relaxing viscous solvents, will result in the loss of ergodicity of the system and in the breakdown of the equilibrium description of the reaction activation barrier (in contrast to the alteration of the rate preexponent in the Kramers description).…”

Section: Introductionmentioning

confidence: 99%

Reorganization Energy of Electron Transfer in Viscous Solvents above the Glass Transition

Ghorai

Matyushov

2006

J. Phys. Chem. B

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We present a molecular-dynamics study of the solvent reorganization energy of electron transfer in supercooled water. We observe a sharp decrease of the reorganization energy at a temperature identified as the temperature of structural arrest due to cage effect as discussed by the mode coupling theory. Both the heat capacity and dielectric susceptibility of the pure water show sharp drops at about the same temperature. This temperature also marks the onset of the enhancement of translational diffusion relative to rotational relaxation signaling the breakdown of the Stokes-Einstein relation. The change in the reorganization energy at the transition temperature reflects the dynamical arrest of the slow, collective relaxation of the solvent related to Debye relaxation of the solvent dipolar polarization.

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Solvent Effects in Nonadiabatic Electron‐Transfer Reactions: Theoretical Aspects

Cited by 120 publications

References 122 publications

Effect of the excitation pulse carrier frequency on the ultrafast charge recombination dynamics of donor-acceptor complexes: Stochastic simulations and experiments

Effect of the excitation pulse carrier frequency on the ultrafast charge recombination dynamics of donor-acceptor complexes: Stochastic simulations and experiments

On the Coherent Description of Diffusion‐Influenced Fluorescence Quenching Experiments II: Early Events

Reorganization Energy of Electron Transfer in Viscous Solvents above the Glass Transition

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