Inner reorganization

Gas-phase nitration is important from theoretical and practical points of view. In solution, the solvation of the small nitronium ion should exceed that of the large aromatic cation-radical, and hence electron transfer should be less probable. In the gas-phase process, the solvation is absent and only inner reorganization energy remains significant. 

The conformational changes also explain the slow electron transfer between two hydrazine moieties separated by a bridge (Gleiter et al. 1996, Nelsen et al. 1975, 1976, 1997b). In all the cases, the inner reorganization energy is high when electron transfer occurs. Particularly, when the unpaired electron is transferred from the planar hydrazine cation-radical unit to the tetrahedral... 

Electron transfer is often associated with the conformational changes. For organic ion-radicals the inner reorganization energies remain modest, allowing a fast passage between the different conformations during the electron transfer (e.g., see Bellec et al. 2000). 

Results from the dissociative reduction of aryl ethers led to a number of important generalizations. These are classical stepwise systems initially forming jr -type radical anions. In this case, the intrinsic barriers for the formation of the intermediate radical anions are dominated by solvent reorganization with only a small (sometimes negligible) contribution from internal reorganization. Thus, the ETs to these systems are properly described by Marcus theory, in which the harmonic approximation satisfactorily accounts for both outer and inner reorganization factors. On the... 

Mu and Schulz [176] have shown that chloro(tetraphenylporphinato)man-ganese(III) complex, in one electron reduction in six aprotic solvents exhibits a dynamic solvent effect, though its inner reorganization energy is larger than the outer... 

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