Electron transfer charge separation/recombination

Figure 1. Schematic energy level diagram for a typical photoinduced electron transfer. Charge separation and recombination routes are shown—see text.

Fig. 16.8 Charge recombination lifetimes in the compounds shown in the inset in dioxane solvent. (J. M. Warman, M. P. de Haas, J. W. Verhoeven, and M. N. Paddon-Row, Adv. Chem. Phys. 106, Electron transfer—from isolated molecules to bio-molecules, Part I, edited by J. JortnerandM. Bixon (Wiley, New York, 1999). The technique used is time-resolved microwave conductivity (TRMC), in which the change in dielectric response of a solution is monitored following photoinduced electron transfer—a charge separation process that changes the solute molecular dipole. The lifetimes shown as a function of bridge length (number of a-bonds separating the donor and acceptor sites in the compounds shown in the inset) are for the back electron transfer (charge recombination) process.

Although the electrostatic potential on the surface of the polyelectrolyte effectively prevents the diffusional back electron transfer, it is unable to retard the very fast charge recombination of a geminate ion pair formed in the primary process within the photochemical cage. Compartmentalization of a photoactive chromophore in the microphase structure of the amphiphilic polyelectrolyte provides a separated donor-acceptor system, in which the charge recombination is effectively suppressed. Thus, with a compartmentalized system, it is possible to achieve efficient charge separation. 

Recently, photochemical and photoelectrochemical properties of fullerene (Cto) have been widely studied [60]. Photoinduced electron-transfer reactions of donor-Qo linked molecules have also been reported [61-63]. In a series of donor-Cfio linked systems, some of the compounds show novel properties, which accelerate photoinduced charge separation and decelerate charge recombination [61, 62]. These properties have been explained by the remarkably small reorganization energy in their electron-transfer reactions. The porphyrin-Qo linked compounds, where the porphyrin moieties act as both donors and sensitizers, have been extensively studied [61, 62]. 

The mere exposure of diphenyl-polyenes (DPP) to medium pore acidic ZSM-5 was found to induce spontaneous ionization with radical cation formation and subsequent charge transfer to stabilize electron-hole pair. Diffuse reflectance UV-visible absorption and EPR spectroscopies provide evidence of the sorption process and point out charge separation with ultra stable electron hole pair formation. The tight fit between DPP and zeolite pore size combined with efficient polarizing effect of proton and aluminium electron trapping sites appear to be the most important factors responsible for the stabilization of charge separated state that hinder efficiently the charge recombination. 

Schlag, E. W., and Levine, R. D. (1992), Ionization, Charge Separation, Charge Recombination and Electron Transfer in Large Systems, J. Phys. Chem. 96, 10608. 

Substitution of zinc(ll) ions into cytochrome c peroxidase (ZnCcP) has been used to exploit photoactivation of electron transfer (eT) reactions since the mid-1990s. The ZnCcP triplet state ( ZnCcP) reduces Fe(III) cytochrome c, and then back electron transfer recombines the charge separation to complete the catalytic cycle (see Figure 7.36). 

Since the values of i/ depend on several factors noted above, in the absence of additional data such as the temperature dependence of the electron transfer rate constants for i-2 it is difficult to analyze the apparent difference between i/ for the charge separation reaction and that of the radical ion pair recombination reaction. However, the difference between these two values of u is not unreasonable given that the charge separation involves oxidation of an excited state of the donor, while radical ion pair recombination involves two ground state radicals. Small changes in the nuclear coordinates of the donor and acceptor for these two reactions should be sufficient to produce the observed difference in i/. The electronic coupling factor between ZnTPP and AQ should be different than that between ZnTPP " and AQ". 

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