Marcus theory, of electron transfer

Samec Z, Weber J (1973) The influence of chemisorbed sulfur on the kinetic parameters of the reduction of Fe " ions on a platinum electrode on the basis of the Marcus theory of electron transfer. J Electroanal Chem Interfacial Electrochem 44 229-238... 

In summary, to apply the Marcus theory of electron transfer, it is necessary to see if the temperature dependence of the electron transfer rate constant can be described by a function of the Arrhenius form. When this is valid, one can then determine the activation energy AEa only under this condition can we use AEa to determine if the parabolic dependence on AG/ is valid and if the reaction coordinate is defined. 

In our description of the Marcus theory of electron-transfer reactions we have found it helpful to plot the free energy change in the three dimensional picture shown in Fig. 10 (Albery, 1975c, 1980). This picture emphasizes that... 

Electron Transfer Far From Equilibrium. We have shown how the Marcus Theory of electron transfer provides a quantitative means of analysis of outer-sphere mechanisms in both homogeneous and heterogeneous systems. It is particularly useful for predicting electron transfer rates near the equilibrium potential,... 

A well defined theory of chemical reactions is required before analyzing solvent effects on this special type of solute. The transition state theory has had an enormous influence in the development of modern chemistry [32-37]. Quantum mechanical theories that go beyond the classical statistical mechanics theory of absolute rate have been developed by several authors [36,38,39], However, there are still compelling motivations to formulate an alternate approach to the quantum theory that goes beyond a theory of reaction rates. In this paper, a particular theory of chemical reactions is elaborated. In this theoretical scheme, solvent effects at the thermodynamic and quantum mechanical level can be treated with a fair degree of generality. The theory can be related to modern versions of the Marcus theory of electron transfer [19,40,41] but there is no... 

The basic assumption of the Marcus theory of electron transfer is that only a weak interaction between the reactants is needed in order for a simple electron-transfer process to occur. Marcus theory considers... 

Fig. 9 Test of the Marcus theory of electron transfer where fcca,c for the cross-reaction O, + R - R, + On is calculated from the thermodynamic free energies and the free energies of activation of the symmetrical reactions. The symbols are as follows O, Ce(IV), x IrCl -, + Mo(CN)j-, Fe(CN) ", R O, Fe(CN)J , A Mo(CN)f, W(CN)<-...

The plateau in Fig. 13.9 corresponds to the diffusion-limited region where the rate of electron transfer is faster than the rate of diffusion. According to the Marcus theory of electron transfer, the observed rate constant of an intermolecular electron transfer is given by [23]... 

The dependence of intervalence transition energy on the activation barrier to thermal electron transfer in Eqs. (1) and (3) allows the solvent dependence of intervalence transitions to be understood in terms of relationships developed for the Marcus Theory of electron transfer (5, 6). 

Marcus theory of electron transfer (Eq. 4) [91] to the rate of electron transfer from ferrocyanide to HRP compound I (8 x 10 M s ) [105], An even larger reorganization energy (2 = 78.0 kcal mol ) [104] was derived from the electron self-exchange rate between HRP compound II and ferric HRP (4.9 x 10 m s ) [104], The extremely large 2 value (78.0 kcal mol ) for the metal-centered electron-exchange between HRP compound II (Fe ) and ferric HRP (Fe ) is consistent with the large... 

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