Method for the evaluation of the reorganization energy of electron transfer reactions in water–methanol mixtures

Pérez, Francisco F. García; Hernández, María del Pilar; Prado‐Gotor, Rafael; Lopes-Costa, Tânia; López‐Cornejo, Pilar

doi:10.1016/j.cplett.2005.03.105

Cited by 5 publications

(5 citation statements)

References 24 publications

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“…It is often attributed to changes in the geometry of the individual molecules and the polarization of the surrounding medium. [34][35][36][37] Recent theoretical calculations have demonstrated that the polarization contribution to reorganization energy is negligible for organic solids.…”

Section: Reorganization Energymentioning

confidence: 99%

Theoretical study on the charge transport property of Pt(CNtBu)2(CN)2 nanowires induced by Pt⋯Pt interactions

Zhao

Yang

et al. 2012

Dalton Trans.

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To deeply understand the charge-transporting nature of Pt(CN(t)Bu)(2)(CN)(2) nanowires induced by intermolecular Pt···Pt interactions, calculations based on first-principle band structure and Marcus theory have been performed. The calculated bandwidths of the valence band, conducting band, and the effective masses of hole and electron are almost equal. This suggests that this complex has ambipolar transport characteristics, in agreement with experimental results. Density of states analysis revealed that the hole transport resulted mainly from the Pt···Pt interactions, while the electron transport was derived mainly from the CN groups. The character of the frontier molecular orbitals, reorganization energies and transfer integrals in different directions also supports the calculated first-principle band structure. Moreover, an investigation into the intermolecular interaction energy of neighbors revealed that there is a remarkable relationship between the intermolecular interaction energy and the transfer integral.

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Section: Reorganization Energymentioning

confidence: 99%

Theoretical study on the charge transport property of Pt(CNtBu)2(CN)2 nanowires induced by Pt⋯Pt interactions

Zhao

Yang

et al. 2012

Dalton Trans.

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“…The dependence of solvent reorganization on the composition of various mixed solvents was thoroughly investigated for a number of homogeneous ET reactions in works. − 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. The nonlinear dependence of λ s in aqueous solutions on the concentration of cosolvent discussed in ref looks qualitatively similar to that suggested by us (see eq ).…”

Section: Model and Computational Detailsmentioning

confidence: 99%

Interplay between Solvent Effects of Different Nature in Interfacial Bond Breaking Electron Transfer

et al. 2009

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Solvent dynamics effects on electroreduction of peroxodisulphate anion on mercury electrode (a typical bond breaking electron transfer reaction) are explored in the framework of the Sumi-Marcus model. The reaction three-dimensional free energy surface is constructed using the Anderson model Hamiltonian. A new interpretation of short- and long-time survival times is presented as well. Since the reduction is assumed to proceed from aqueous sucrose and glucose solutions of different concentrations (which are used to vary the solution viscosity), unavoidable changes in the Pekar factor (static effect) are also taken into account. The results of model calculations are employed to interpret challenging experimental data on nonmonotonous constant rate vs solution viscosity dependence reported earlier (in part, appearance of an ascent plot). The influence of mixed solvent composition on the reaction rate and transfer coefficient is explained in terms of the saddle point avoidance in the vicinity of activationless discharge. Splitting of the reaction coordinates into slow (solvent) and fast (intramolecular) ones is argued to be crucial, as the most important reaction features cannot be described by means of more simplified models, even if both static and dynamic effects are addressed.

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“…Redox reactions at the interface of an active protein to water might be another example of systems, where nonlinear effects (nongauss fluctuations of solvent molecules) take place . Nevertheless, the solvent reorganization energy still remains a convenient and commonly adopted language to describe the Franck–Condon barrier in homogeneous electron-transfer reactions in mixed solvents. − It is important to note that in this work we are interested first of all in addressing the qualitative behavior of the solvent reorganization energy as a function of the EG content in solutions; this justifies to some extent the simplified approach used to estimate the λ s values (eqs , ).…”

Section: Computational Detailsmentioning

confidence: 99%

“…Because solvent reorganization energy is an important parameter in the above-mentioned calculations, it is therefore worth it to go beyond simplified continuum approaches and to describe a possible “static” solvent effect in water–EG solutions at the reduction of S 2 O 8 2– at atomistic level. 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. − 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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Method for the evaluation of the reorganization energy of electron transfer reactions in water–methanol mixtures

Cited by 5 publications

References 24 publications

Theoretical study on the charge transport property of Pt(CNtBu)2(CN)2 nanowires induced by Pt⋯Pt interactions

Theoretical study on the charge transport property of Pt(CNtBu)2(CN)2 nanowires induced by Pt⋯Pt interactions

Interplay between Solvent Effects of Different Nature in Interfacial Bond Breaking Electron Transfer

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

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