The Theory of Electron Transfer Reactions:  What May Be Missing?

Small, David W.; Matyushov, Dmitry V.; Voth, Gregory A.

doi:10.1021/ja029595j

Cited by 160 publications

(218 citation statements)

References 104 publications

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“…13,18,51 The solute is also nonpolarizable and rigid. Polarizability [16][17][18] and flexibility 52,53 of the solute, which in principle can be incorporated in computer simulations, are still computationally expensive when the entropy of reorganization is concerned. Our analysis is therefore limited to the thermodynamics of interactions between partial charges of the solute and the solvent.…”

Section: Introductionmentioning

confidence: 99%

Solvent Reorganization Entropy of Electron Transfer in Polar Solvents

2006

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We report the results of molecular dynamics simulations of the solvent reorganization energy of intramolecular electron transfer in a charge-transfer molecule dissolved in water and acetonitrile at varying temperatures. The simulations confirm the prediction of microscopic solvation theories of a positive reorganization entropy in polar solvents. The results of simulations are analyzed in terms of the splitting of the reorganization entropy into the contributions from the solute-solvent interaction and from the alteration of the solvent structure induced by the solute. These two contributions mutually cancel each other, resulting in the reorganization entropy amounting to only a fraction of each component.

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Section: Introductionmentioning

confidence: 99%

Solvent Reorganization Entropy of Electron Transfer in Polar Solvents

2006

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“…[9][10][11] Two notable discrepancies have been known in the literature. First, computer simulations indicated that the solvent reorganization energy depends on the charges of the donor-acceptor system, [12][13][14][15][16][17][18] not only on the amount of charge transfer as predicted by the Marcus theory.…”

Section: Introductionmentioning

confidence: 99%

“…Second, timeresolved spectroscopic measurements of electron-transferring species revealed differences in the energies and shapes of the absorption and the emission bands, while the Marcus picture predicts a perfect symmetry between the two bands. 11,19,20 The explanation of these phenomena requires theoretical methods a) Electronic mail: zgw@cheme.caltech.edu that account for solvent properties beyond the linear dielectric approximation, such as spatially varying dielectric response and dielectric saturation.…”

Section: Introductionmentioning

confidence: 99%

A molecularly based theory for electron transfer reorganization energy

Zhuang

Wang

2015

The Journal of Chemical Physics

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Articles you may be interested inUsing field-theoretic techniques, we develop a molecularly based dipolar self-consistent-field theory (DSCFT) for charge solvation in pure solvents under equilibrium and nonequilibrium conditions and apply it to the reorganization energy of electron transfer reactions. The DSCFT uses a set of molecular parameters, such as the solvent molecule's permanent dipole moment and polarizability, thus avoiding approximations that are inherent in treating the solvent as a linear dielectric medium. A simple, analytical expression for the free energy is obtained in terms of the equilibrium and nonequilibrium electrostatic potential profiles and electric susceptibilities, which are obtained by solving a set of self-consistent equations. With no adjustable parameters, the DSCFT predicts activation energies and reorganization energies in good agreement with previous experiments and calculations for the electron transfer between metallic ions. Because the DSCFT is able to describe the properties of the solvent in the immediate vicinity of the charges, it is unnecessary to distinguish between the inner-sphere and outer-sphere solvent molecules in the calculation of the reorganization energy as in previous work. Furthermore, examining the nonequilibrium free energy surfaces of electron transfer, we find that the nonequilibrium free energy is well approximated by a double parabola for self-exchange reactions, but the curvature of the nonequilibrium free energy surface depends on the charges of the electron-transferring species, contrary to the prediction by the linear dielectric theory. C 2015 AIP Publishing LLC. [http://dx

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“…14, 27 The main property of interest in that problem is the equilibrium distribution P (Ω) of the transition frequency Ω. The rate of an electron-transfer reaction is proportional to the probability P (0) of radiationless transition at Ω = 0.…”

Section: Introductionmentioning

confidence: 99%

“…Following our early studies of electron-transfer reactions, 27 we consider a single solute carrying the dipole moment and polarizability. Both change with the electronic transition.…”

Section: Introductionmentioning

confidence: 99%

Non-Gaussian Lineshapes and Dynamics of Time-Resolved Linear and Nonlinear (Correlation) Spectra

Dinpajooh

Matyushov

2014

J. Phys. Chem. B

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Signatures of nonlinear and non-Gaussian dynamics in time-resolved linear and nonlinear (correlation) 2D spectra are analyzed in a model considering a linear plus quadratic dependence of the spectroscopic transition frequency on a Gaussian nuclear coordinate of the thermal bath (quadratic coupling). This new model is contrasted to the commonly assumed linear dependence of the transition frequency on the medium nuclear coordinates (linear coupling). The linear coupling model predicts equality between the Stokes shift and equilibrium correlation functions of the transition frequency and time-independent spectral width. Both predictions are often violated, and we are asking here the question of whether a nonlinear solvent response and/or non-Gaussian dynamics are required to explain these observations. We find that correlation functions of spectroscopic observables calculated in the quadratic coupling model depend on the chromophore's electronic state and the spectral width gains time dependence, all in violation of the predictions of the linear coupling models. Lineshape functions of 2D spectra are derived assuming Ornstein-Uhlenbeck dynamics of the bath nuclear modes. The model predicts asymmetry of 2D correlation plots and bending of the center line. The latter is often used to extract two-point correlation functions from 2D spectra. The dynamics of the transition frequency are non-Gaussian. However, the effect of non-Gaussian dynamics is limited to the third-order (skewness) time correlation function, without affecting the time correlation functions of higher order. The theory is tested against molecular dynamics simulations of a model polar-polarizable chromophore dissolved in a force field water.

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The Theory of Electron Transfer Reactions: What May Be Missing?

Cited by 160 publications

References 104 publications

Solvent Reorganization Entropy of Electron Transfer in Polar Solvents

Solvent Reorganization Entropy of Electron Transfer in Polar Solvents

A molecularly based theory for electron transfer reorganization energy

Non-Gaussian Lineshapes and Dynamics of Time-Resolved Linear and Nonlinear (Correlation) Spectra

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