Sphere Rearrangement With Flow of Charge

Inner Sphere Rearrangement With Flow of Charge  

As before, -(AEijZ- AEj z q) + q(AEiiZ AEi z ) can be expanded as far as the quadratic terms the energy change along the reaction coordinate above the ground states of the reactants and products in equilibrium. The first two binomial terms vanish, so  

Again q = 1/2, so AEj = -AEj z[n/4(n - 2)2z2] and is rather small (7-11 kJ/mole). Hush considered AEj to be 50% of the total activation energy, the remainder being Outer Continuum energy. Since it again contains q(l - q), introduction of the overpotential as before again gives a symmetry factor (C + fri)/2C, where 

In his 1961 paper,67 Hush modified his outer sphere energy equation by changing the (1 - l/s0) term to the Marcus expression (1/n2 - 1/e0) because the electron transition time, though longer than that under FC conditions, would still be short compared to solvent molecule motion. This proposition will be discussed later. The q value 

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