Reorganisation energy Outer-sphere

However, to get a crude feeling about the relation between the calculated and measured reorganisation energies, we can proceed in the following way. The outer-sphere reorganisation energy of three tentative configurations of the dock-... 

Figure 93 Three-step mechanism for outer-sphere electron-transfer reactions. Line 1. Chemical species and processes. Line 2. R are the reactants I is the precursor intermediate complex I is the successor intermediate complex P are the products j is the activated complex. Line 3. a is the association to I et is the electron-transfer step d is the dissociation of I to products b, c is the ligand and solvent reorganisation. Line 4. Free-energy changes.

In general terms, the theory of Marcus involves a model for ET reactions based on the approximation that the inner-coordination sphere energy is independent of the outer-sphere reorganisation. In its classical formulation, TM provides the rate for a self-exchange reaction such as reaction (16.1)... 

---