FLUX-FORCE FORMALISM FOR CHARGE-TRANSPORT DYNAMICS IN SUPRAMOLECULAR STRUCTURES - 2 - DIFFUSIVITY AND ELECTRONEUTRALITY COUPLING EFFECTS

The conductance and transport number expressions are derived for the i on-involved electron-hopping (IIEH) mechanism taking into account the ion pairing between fixed redox ions and the mobile electroinactive co unterions. Under the steady-state condition, the effects of ion pairin g, the ratio of diffusivity associated with electron hopping and the m obile electroinactive counterion, and the applied potential are studie d both in the presence and in the absence of supporting electrolyte, T he main effect of ion pairing is to decrease the charge transport rate , and that of the diffusivity rake is to change the mechanism of the c onductance process from ohmic (electronic) to redox (or nonohmic). Thi s change in the conductance behavior from ohmic to nonohmic is shown t o be due to the change in the rate-limiting process from electron tran sport to counterion movement. A direct correlation between the propose d theory and experimental results obtained earlier using poly(benzimid azobenzophenanthroline) and [Os(vbpy)(3)](2+)/[Zn(vbpy)(3)](2+) copoly mer coated electrodes is demonstrated.