Free energy of photoinduced electron transfer

Nucleobases can serve as either electron donors or electron acceptors in photo-induced electron transfer reactions with electronically excited acceptors (Ac) or donors (D), respectively. The free energy of photoinduced electron transfer reaction in which the nucleobase (N) serves as a donor or acceptor can be estimated using the Rehm-Weller equations (Eqs. 5 and 6), respectively. 

Coinitiators according to route A are electron-deficient materials. Representative examples are onium compounds and triazines [269, 563], The free energy of photoinduced electron transfer (AGei) between a photosensitizer and a coinitiator is described by Eq. (64), in which /i, /2 is the half-wave oxidation potential (route A e J2 is representative for the sensitizer route B Fox" stands for the coinitiator), is the half-wave reduction potential (route A red is representative for the coinitiator route B stands for the sensitizer), and oo is the... 

The mechanism of quenching had previously been established by observing the formation of free radical ions using flash photolysis.345 Rehm and Weller proposed the empirical Equation 5.5 to fit the data, where AetG° is the free energy of photoinduced electron transfer in the contact pair (Equation 5.1), AG is the free energy of activation that accounts for the structural and solvent reorganization required for the transfer of an electron, kd and k d are the rate constants for the formation and separation of the encounter complex, respectively, Kd = kd/k d is the equilibrium constant of complex formation and Z is the bimolecular collision frequency in an encounter complex, Z 1011 s 346 A value of kd/(ZKd) = 0.25 was used. 

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