FLUX-FORCE FORMALISM FOR CHARGE-TRANSPORT DYNAMICS IN SUPRAMOLECULAR STRUCTURES - 1 - ACTIVITY-COEFFICIENT AND INTERACTION ENERGY CONSIDERATIONS

A comprehensive analysis starting from the formalism of irreversible t hermodynamics, incorporating activity coefficients and interparticle i nteractions, is developed to derive expressions for mixed conductance, transport numbers, etc., for diffusive and electric field assisted el ectron hopping through polymer matrixes attached to electrode surfaces . The transport equation obtained is a combination of Dahms-Ruff diffu sion and the Levich migration terms and includes short-range interpart icle interactions under molecular field approximation as well as activ ity coefficient terms. The derived dynamical equation for electron flu x follows a second-order law in species concentrations in contrast to the classical Nemst-Planck equation for ion migration. Applicable syst ems are thought to be organic pi-conjugated electroactive polymers, el ectronically conducting polymers with covalently linked redox groups, i.e., metal ion redox site membranes, and ion-exchange polymers. The c oncept of self and tracer diffusion coefficients is brought into the f ormalism of charge transport in supramolecular structures. Some new in sights regarding the identification of Onsager's coefficient in diffus ion through supramolecular structures are also provided.