Correlations reorganizational energy

The approximate linear decrease of reorganizational energies with increasingly larger 8ch energies (Eig. 12.2) and Eq. (12.11) explain the existence of a correlation between Dch and sch-... 

Figure 6 The correlation, based on equation (61), of the absorption maxima of ion-pair charge transfer transitions to the difference in reduction potentials and the average of the reorganizational energies of the constiment electron-transfer couples. , Ru " with...

The energy of an optical electron transfer transition, E p, is correlated according to Hush theory [24,25] to the energy gradient between the minima of the A.B and curves, AE, and to the reorganizational energy, X (eq 2). Detailed expressions for the calculation of 1 in terms of... 

X /X" reduction potentials in the bound and ion-pair systems. The actual reduction potentials have been measured for some of the (NH3)5Ru "[NCM (CN)5] complexes [83] and estimated for some of the Ru (NH3)5(X ) " complexes. For these complexes, the effective reorganizational free energies are Xp = (5 0 1.4) x 10 cm , independent of whether X is a halide or a hexacyano complex. Similarly, a plausible correlation line can be drawn through the data in Figure 3 with a slope of one and an intercept of —5 x 10 cm. In the Co complexes, the coordinated halide is probably more difficult to oxidize, while the metal is easier to reduce [73, 94] than in the corresponding ion pair, and the effect of the reduction potentials may not be particularly important. A very rough estimate suggests that Xx/Xp ay... 

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