Electron transfer parameters

The partial electron transfer parameter kj is directly related to the dipole moment, Pj, of adsorbed j via ... 

Effect of partial electron transfer parameter Figure 6.23 depicts the effect of the value of the partial charge transfer parameter A,d for fixed XA(= 0.15) on the rate enhancement ratio p(=r/r0) for the four main types of promotional behaviour, i.e., electrophobic, electrophilic, volcano and inverted volcano. The main feature of the Figure is that it confirms in general the global mle... 

The perturbational analysis of the adiabatic surface near the totally symmetric zero point [27] shows that for the realistic values of the electron transfer parameters one of two Alu normal vibrations is much softer than all other vibrations. We can expect that this mode together with two Alg modes play the most important role in the structural distortions and charge redistribution in the cluster. 

CapeillEre-Blandin, C., and Albani, J., 1987, Cytochrome bz, an electron carrier between flavocytochrome 2 and cytochrome c. Rapid kinetic characterisation of the electron transfer parameters with ionic strength dependence, Biochem. J. 245 1599165. 

BASIC CONCEPTS AND SOME PERTURBATION THEORY-BASED RELATIONSHIPS OF ELECTRON-TRANSFER PARAMETERS... 

The differences between the observed electron-transfer parameters (xr, AGda, etc.) and their values for an... 

The Correlation of Observed Ion-Pair Charge-Transfer Energies with Experimental Electron-Transfer Parameters... 

Let us discuss the Robin and Day classification scheme from the point of view of the generalized vibronic model. In the case of strong PKS - coupling (Case 1), depending on the magnitude of the electron transfer parameter, MV compounds can belong to Classes I, II or III. So, when ts — A / 2 the system is... 

Capeillere-Blandin, C. and Albani, J. 1987, Cytochrome b2, an electi on carrier between flavocytochrome b, and cytochrome c Rapid kinetic characterisation of the electron transfer parameters with ionic strength dependence. Biochemical Journal 245, 159-165. Carpita, N. C. and Gibeaut, D. M. 1993, Structural models of primary cell walls in flowering plants consistency of molecular structure with the physical properties of the walls during growth. Plant Journal 3, 1 -30. 

Convergence of spectroscopic and kinetic electron transfer parameters for mixed-valence binuclear dipyridylamide ruthenium amine complexes 05CCR(249)507. 

Wu Q, Van Voorhis T (2006) Direct calculation of electron transfer parameters through constrained density functional theory. J Phys Chem A 110 9212... 

Table 3 Electron transfer parameters for some couples that involve very small molecular reorganizational energies. 

The alterations of some key electron transfer parameters when there is appreciable delocalization of electron density are discussed in Section 7.11.2. These changes to the properties of the ground state can be described in terms of correlated increases in the anharmonicity of the ground state PE surface. Such anharmonicities imply that there are changes in the frequencies of some vibrational modes that are correlated with the reaction coordinate, and that the size of the anharmonic contribution correlates with increases in electron delocalization. 

Table 7 Electron transfer parameters in some donor-acceptor complexes with two atom bridges. 

Chronoabsorptometry has been applied to the determination of heterogeneous electron-transfer parameters in single-step irreversible [55] and quasi-irreversible kinetics [56] and in double potential step modes [57]. In the case of a single potential step for the reaction... 

Duffy JA (1980) Trends in energy gaps of binary compounds an approach based upon electron transfer parameters from optical spectroscopy. J Phys C 13 2979-2990 Mooser E, Pearson WB (1959) On the crystal chemistry of normal valence compounds. Acta Cryst 12 1015-1022... 

Curves in Figs. 12A and B assume a reversible preceding chemical step and the chemical equilibrium shifted towards the inactive species Y (K 1). Curve 1 represents a CV voltammogram of the diffusion-controlled reversible electron transfer. Both the kinetic parameter X = ks/cr and electron transfer parameter A = kh(Dcr) - are high. Ip f and Ip b are the same. Curve 2 characterizes the irreversible electron transfer... 

A kinetic sigmoidal wave (curve 3 in Fig. 12B) indicates low values of 2 at high values of electron transfer parameter A). The current tends towards the limiting value given by the equation... 

TABLE 5. Electron transfer parameters for class II mixed-valence compounds. 

Following Bard and Faulkner (2001), for the reaction with the RDS involving single-electron transfer, parameter a is 0.5. Measurements (Holtappels et al., 1999) gave a 0.7 however, to simplify calculations we will adopt the value 0 = 1 — a = 0.5. Note that this choice of a is important only in the region of small currents, when both exponents in the Butler-Volmer equation contribute to the activation polarization. At larger currents the second exponent in Eq. (4.153) is small and the results below are valid for arbitrary a. 

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