Reorganisation energies

Reorganisation energies of optical electron transfer processes. R. D. Cannon, Adv. Inorg. Chem. Radiochem., 1978, 21 179-230 (155). 

The potential energy surfaces on which the electron-transfer process occurs can be represented by simple two-dimensional intersecting parabolic curves (Figure 6.23). These quantitatively relate the rate of electron transfer to the reorganisation energy (A.) and the free-energy changes for the electron-transfer process (AG°) and activation (AG ). 

The reorganisation energy consists of internal Ai and solvent As contributions. The former can be calculated in the Born-Hush approach via [107,109,119]... 

Table 1.4. Reorganisation energy A, free energy change AGCS and barrier AG)S for intramolecular electron transfer in OPVn-Ceo dyads in different solvents relative to the energies of the OPVn(5i) and MP Ceo(Si) states...

The non-adiabatic charge separation rate constant is a function of the energy barrier AGjs, the reorganisation energy, and the electronic coupling V between donor and acceptor in the excited state [120] ... 

Beekman et al., 1996 Jia et at., 1993). An analysis with the classical Marcus function of the relationship between the measured In( gj) and a A G for the reaction that was inferred from a measured value for E P/P", yielded a reasonable fit and a rather small reorganisation energy of 30meV for the primary reaction. 

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