Basic Electron-Transfer Theory

Bolton, James R.; Archer, Mary D.

doi:10.1021/ba-1991-0228.ch002

Cited by 87 publications

(106 citation statements)

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“…19,20,23 Since that time, his expression has been used to effectively describe electron transfer under a variety of conditions. 24,25 The rate of electron transfer, k(r), can be written where r is the distance between the centers of the donor and acceptor molecules and r o is the distance at which the donor and acceptor hard spheres are in contact. J o is the contact value of the donor/acceptor electronic coupling matrix element, and characterizes the distance dependence of the coupling.…”

Section: Theorymentioning

confidence: 99%

“…24 Determination of these values for the heterogeneous DNA environment follows the method developed by Weller for calculating redox potentials in one bulk solvent when redox potentials are known in a solvent with different dielectric properties. 29 Following this method, ∆G in a DNA duplex can be calculated from oxidation/reduction potentials measured in bulk solution.…”

Section: Theorymentioning

confidence: 99%

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Distance Dependence of Electron Transfer in DNA: The Role of the Reorganization Energy and Free Energy

2000

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A model of the distance dependence of photoinduced donor-acceptor electron transfer in DNA is presented that includes the distance dependence of the solvent reorganization energy and free energy in the heterogeneous DNA environment. DNA is modeled as a low dielectric region that represents the base stack and two regions with more moderate dielectric properties that represent the DNA backbone. The DNA is surrounded by a high dielectric medium, which represents water. Model calculations show the importance of including the reorganization energy and the free energy change and illustrate the differences between the inhomogeneous model and homogeneous single dielectric constant calculations using standard Marcus theory. Calculations are performed for comparison to published experimental work (Science 1997, 277, 673; 1 J. Am. Chem. Soc. 1992, 114, 3656 2 ). Fits to one set of data 2 permit the previously reported distance dependence to be separated into an electronic contribution and solvent reorganization energy and free energy contributions. For the other set of data, 1 inclusion of the solvent reorganization energy and free energy distance dependences in the analysis of the overall distance dependent data suggest that the Marcus form of the distance dependent rate constant including the Marcus reorganization energy is not consistent with the data.

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Section: Theorymentioning

confidence: 99%

Section: Theorymentioning

confidence: 99%

Distance Dependence of Electron Transfer in DNA: The Role of the Reorganization Energy and Free Energy

2000

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“…Here V is the electronic coupling coefficient, l is the reorganization energy and DG " is the free energy of activation of the electron transfer [58], for which the relation…”

Section: Electron Transfer Quenchingmentioning

confidence: 99%

Ligand dependence of magnetic spin effects on photooxidation of [Ru(bpy)3−n(CN)2n](+2−2n) type complexes

Fodor

Ülveczki

Horváth

et al. 2002

Inorganica Chimica Acta

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Photoinduced electron transfer reaction from the series of [Ru(bpy) (3(n ) (2'(2n ) complexes (n0/0, 1, 2) to methylviologen has been investigated using external magnetic field modulation in order to obtain relevant kinetic parameters for spin relaxation, backward electron transfer and cage escape of the geminate radical pair. The replacement of one bpy by two cyanide ligands results in an increase of the quenching rate constant and a decrease of the cage escape efficiency. The latter is decreased in a magnetic field and the sensitivity of this effect is weakened by introducing CN ( ligands. From the analysis of the magnetic field dependence it can be inferred that with increasing number of CN ( ligands, backward electron transfer rate and spin relaxation time in the geminate radical pair exhibit a moderate decrease but that the rate constant of cage escape decreases very strongly. #

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“…γ can be used to obtain the cord length, r. The form developed by Marcus in the 1950s for the distancedependent rate coefficient for nonadiabatic electron transfer in the normal regime has been proven to be accurate in a wide variety of systems. 49,50 For the type of micelle systems under consideration here, the Marcus transfer rate can be written as a function of γ: 2,3,51 where γ is the angle between the lines joining the donor and acceptor molecules on the micelle surface to the micelle center ( Figure 1B). γ o , which accounts for donor-acceptor excluded volume, is the angle at which the donor and acceptor hard spheres are in contact.…”

Section: Theorymentioning

confidence: 99%

Solvent Reorganization Energy and Free Energy Change for Donor/Acceptor Electron Transfer at Micelle Surfaces: Theory and Experiment

et al. 1998

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Theories are presented for calculating the solvent reorganization energy and the free energy change which occur in photoinduced donor/acceptor electron transfer at the surface of micelles. The theories are based on the Marcus theory for spherical reactants in a dielectric continuum. The micelle is modeled with regions of differing dielectric properties, representing the micelle core, the headgroup region, and the surrounding water. The free energy change accompanying electron transfer can be calculated from redox measurements made in bulk liquids. The theories are applied to previously published photoinduced intermolecular electron-transfer data between octadecylrhodamine B (ODRB) and N,N-dimethylaniline (DMA) molecules.1 The ODRB and DMA molecules are located in the surface region of three different types of surfactant micelles: dodecyl-, tetradecyl-, and cetyl-trimethylammonium bromide (DTAB, TTAB, and CTAB, respectively). The data show an increased rate of electron transfer with increasing micelle radius. Application of the new theory to the electron-transfer data along with information provided by neutron scattering experiments show that the headgroup regions of the three micelles have different dielectric constants because water penetration into the headgroup regions decreases as the surfactant length increases.

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Basic Electron-Transfer Theory

Cited by 87 publications

References 0 publications

Distance Dependence of Electron Transfer in DNA: The Role of the Reorganization Energy and Free Energy

Distance Dependence of Electron Transfer in DNA: The Role of the Reorganization Energy and Free Energy

Ligand dependence of magnetic spin effects on photooxidation of [Ru(bpy)3−n(CN)2n](+2−2n) type complexes

Solvent Reorganization Energy and Free Energy Change for Donor/Acceptor Electron Transfer at Micelle Surfaces: Theory and Experiment

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