Excitation transfer diffusion limitations

It is clear that one of the major limitations of this analysis is the assumption of constant excited-state coverage. Deviations from the behavior described by Eq. (45) in the low frequency range have been observed at photocurrent densities higher than 10 Acm [50]. These deviations are expected to be connected to excited-state diffusion profiles similar to those considered by Dryfe et al. [see Eq. (38)] [127]. A more general expression for IMPS responses is undoubtedly required for a better understanding of the dynamics involved in back electron transfer as well as separation of the photoproducts. 

The presence of a base is also essential for the efficient reductive dehalogenation of RX by 1-benzyl-1,4-dihydronicotinamide (BNAH) via photoinduced electron transfer [121,122], Since the one-electron oxidation potential of the singlet excited state of BNAH ( BNAH ) is —3.1 V (vs. SCE) [50], which is more negative than the one-electron reduction potential of benzyl bromide (PhCH2Br), photoinduced electron transfer from BNAH to PhCH2Br occurs efficiently with the diffusion-limited rate [122]. This fast process needs no base catalyst to accelerate the electron transfer rate further. However, the photoinduced electron transfer results in... 

For many energy transfer processes, the interaction takes place when the partners are separated by more than the sum of the gas-kinetic collision radii. For example, energy transfer between excited singlet states of hydrocarbons occurs as fast as spontaneous decay at concentrations in benzene corresponding to a distance, r, between exchanging molecules of about 5 nm, or about 10 times the collision diameter. The measured rate constants for transfer of excitation in the hydrocarbons also seem greatly to exceed the diffusion-limited rate, and do not depend on solvent viscosity. 

Quenching of excited-state [Ru(bipy)3] by reduced blue proteins involves electron transfer from the Cu with rate constants close to the diffusion limit for electron-transfer reactions in aqueous solution. It is suggested that the excited Ru complex binds close to the copper-histidine centre, and that outer-sphere electron transfer occurs from Cu through the imidazole groups to Ru. Estimated electron-transfer distances are about 3.3 A for plastocyanin and 3.8 A for azurin, suggesting that the hydrophobic bipy ligands of Ru " penetrate the residues that isolate the Cu-His unit from the solvent. ... 

The third type of behavior for these systems is seen when the excited state electron transfer becomes much more favorable and kq approaches the diffusion limit. For example, [Cu(dpp)2] quenching by Cr(hfac)3 (hfac = hexafloroacetylaceto-... 

More related to general photochemistry are the papers which have appeared on wholly or partly diffusion-controlled reactions. The effect of a very short lifetime of the donor on the calculation of fluorescence quantum yields and lifetimes has been analysed by Viriot et al. Andre et al. analyse the kinetics of energy transfer to an acceptor when there are two different excited states capable of acting as donors and when interaction between these states is possible. The exchange interaction contribution to energy transfer between ions in the rapid diffusion limit... 

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