Reorganization energy intramolecular

The change in the inner-sphere structure of the reacting partners usually leads to a decrease in the transition probability. If the intramolecular degrees of freedom behave classically, their reorganization results in an increase in the activation barrier. In the simplest case where the intramolecular vibrations are described as harmonic oscillators with unchanged frequencies, this leads to an increase in the reorganization energy ... 

An expression of the type in Eq. (29) has been rederived recently in Ref. 13 for outer-sphere electron transfer reactions with unchanged intramolecular structure of the complexes where essentially the following expression for the effective outer-sphere reorganization energy Ers was used ... 

These structural factors are relevant for the redox-activity of bis- and oligo-electrophoric systems and for the reorganization energy associated with intramolecular electron hopping. 

The rate of degenerate intramolecular electron-transfer processes in biselectrophoric redox systems, and the observed spin-density distribution over one or two units depend upon the overall reorganization energy and thus upon... 

Figure 1. Activation energy of electron-transfer process as a function of electronic energy gap of a reaction. Er = Eg + Ec is the total reorganization energy where Es is the classical solvent reorganization energy and Ec is the reorganization energy of an intramolecular mode, l

It was assumed that the electron transfer assisted by the intramolecular mode and polar media requires the reorganization energy... 

As described above, both porphyrins and fullerenes have highly delocalized JT-systems suitable for efficient electron transfer, because the uptake or release of electrons results in minimal structural and solvation changes upon electron transfer to afford small reorganization energies of electron transfer. Therefore, extensive efforts have been devoted to study intramolecular electron transfer in elec-... 

A is the sum of the solvent and intramolecular reorganization energies, and AG = F(A 0 - A 0J) is the standard electrochemical Gibbs energy of the electron transfer from x = a to x = b. Parabolic dependence of AG on AG was demonstrated [viii]. Electrochemical behavior including the kinetic analysis of various ET systems was reviewed [ix]. A special type of the ET reaction is the deposition of a metal at ITIES, e.g., the deposition of Au particles by the interfacial reaction between AUCI4 in 1,2-dichloroethane and Fe(CN)6 in water [x]. 

As demonstrated above, the driving force dependence of / et of the metal ion-promoted intramolecular ET can be evaluated well within the context of the Marcus theory of ET. Here the driving force of MCET increases with increasing concentrations of metal ions, whereas the reorganization energy of MCET decreases with concentrations of metal ions. 

The reorganization energy is usually considered as the sum of intramolecular ( in ) and solvent ( out ) contributions ... 

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