Electron transfer reactions in solvent mixtures: the excess component of solvent reorganization free energy

Morillo, M.; Denk, C.; Pérez, Pilar; López, Miguel Ángel Martín; Sánchez, A.; Prado, R.; Sánchez, Francisco

doi:10.1016/s0010-8545(99)00238-6

Cited by 19 publications

(7 citation statements)

References 61 publications

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“…39 In addition, the framework of the DSCFT can be easily extended to ET reactions in solvent mixtures, where preferential solvation is expected to have significant effects in the solvent reorganization. 57,[81][82][83] We will examine such effects on ET reactions in solvent mixtures in a forthcoming paper.…”

Section: Discussionmentioning

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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Section: Discussionmentioning

confidence: 99%

A molecularly based theory for electron transfer reorganization energy

Zhuang

Wang

2015

The Journal of Chemical Physics

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“…11,[31][32][33][34][35][36][37][38][39][40] Moreover, the kinetic, 35,41 dynamic, 42,43 and spectro-scopic behaviors 44 for ET processes in solvent mixtures cannot be directly correlated with the corresponding properties in the pure solvent components. It is generally recognized that ET in mixed solvents is not controlled by macroscopic solvent parameters because of preferential solvation, 41,[44][45][46][47][48][49][50] as the local composition of the solvent around a charged solute is significantly different from the bulk composition. 51 Despite its importance, there have been very few theoretical studies for ET in liquid mixtures.…”

Section: Introductionmentioning

confidence: 99%

“…However, no systematic trend has emerged for understanding the observed behaviors and for predicting the behaviors in general mixtures. ,− Moreover, the kinetic, , dynamic, , and spectroscopic behaviors for ET processes in solvent mixtures cannot be directly correlated with the corresponding properties in the pure solvent components. It is generally recognized that ET in mixed solvents is not controlled by macroscopic solvent parameters because of preferential solvation, ,− as the local composition of the solvent around a charged solute is significantly different from the bulk composition…”

Section: Introductionmentioning

confidence: 99%

Molecular-Based Theory for Electron-Transfer Reorganization Energy in Solvent Mixtures

Zhuang

Wang

2016

J. Phys. Chem. B

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Using statistical-field techniques, we develop a molecular-based dipolar self-consistent-field theory (DSCFT) for charge solvation in liquid mixtures under equilibrium and nonequilibrium conditions, and apply it to compute the solvent reorganization energy of electron-transfer reactions. In addition to the nonequilibrium orientational polarization, the reorganization energy in liquid mixtures is also determined by the out-of-equilibrium solvent composition around the reacting species due to preferential solvation. Using molecular parameters that are readily available, the DSCFT naturally accounts for the dielectric saturation effect and the spatially varying solvent composition in the vicinity of the reacting species. We identify three general categories of binary solvent mixtures, classified by the relative optical and static dielectric permittivities of the solvent components. Each category of mixture is shown to produce a characteristic local solvent composition profile in the vicinity of the reacting species, which gives rise to the distinctive composition dependence of the reorganization energy that cannot be predicted using the dielectric permittivities of the homogeneous solvent mixtures.

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“…The dependence of solvent reorganization on the composition of various mixed solvents in the regime of homogeneous ET mixed solvents was thoroughly investigated for a number of redox couples in works. 9−13 This quantity was extracted from experimental rate constants as well as estimated using model calculations. The authors put primary attention on the analysis of the Pekar factor as a function of the solution composition (this dependence can be both linear and nonlinear) and concluded that preferential solvation crucially affects the solvent reorganization.…”

Section: Introductionmentioning

confidence: 99%

Interfacial Bond-Breaking Electron Transfer in Mixed Water–Ethylene Glycol Solutions: Reorganization Energy and Interplay between Different Solvent Modes

et al. 2013

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We explore solvent dynamics effects in interfacial bond breaking electron transfer in terms of a multimode approach and make an attempt to interpret challenging recent experimental results (the nonmonotonous behavior of the rate constant of electroreduction of S2O82– from mixed water–EG solutions when increasing the EG fraction; see Zagrebin, P.A. et al. J. Phys. Chem. B2010, 114, 311). The exact expansion of the solvent correlation function (calculated using experimental dielectric spectra) in a series predicts the splitting of solvent coordinate in three independent modes characterized by different relaxation times. This makes it possible to construct a 5D free-energy surface along three solvent coordinates and one intramolecular degree of freedom describing first electron transfer at the reduction of a peroxodisulphate anion. Classical molecular dynamics simulations were performed to study the solvation of a peroxodisulphate anion (S2O82–) in oxidized and reduced states in pure water and ethylene glycol (EG) as well as mixed H2O–EG solutions. The solvent reorganization energy of the first electron-transfer step at the reduction of S2O82– was calculated for several compositions of the mixed solution. This quantity was found to be significantly asymmetric. (The reorganization energies of reduction and oxidation differ from each other.) The averaged reorganization energy slightly increases with increasing the EG content in solution. This finding clearly indicates that for the reaction under study the static solvent effect no longer competes with solvent dynamics. Brownian dynamics simulations were performed to calculate the electron-transfer rate constants as a function of the solvent composition. The results of the simulations explain the experimental data, at least qualitatively.

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Electron transfer reactions in solvent mixtures: the excess component of solvent reorganization free energy

Cited by 19 publications

References 61 publications

A molecularly based theory for electron transfer reorganization energy

A molecularly based theory for electron transfer reorganization energy

Molecular-Based Theory for Electron-Transfer Reorganization Energy in Solvent Mixtures

Interfacial Bond-Breaking Electron Transfer in Mixed Water–Ethylene Glycol Solutions: Reorganization Energy and Interplay between Different Solvent Modes

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