ELECTRON SELF-EXCHANGE IN REDOX POLYMERS - 1 - MECHANISTIC ANALYSIS AND STATISTICAL-MECHANICAL CONSIDERATIONS

A comprehensive analysis of electron hopping between spatially separat ed redox centres pertaining to supramolecular structures is carried ou t by taking into account different mechanistic pathways. Spin exchange dynamics due to Kawasaki is invoked to study the transport phenomena for the more appropriate, thermodynamically favored ion pairing mechan ism. The generalized master equation and its reduced form are presente d and the dynamics of electron hopping is analyzed both under spin-1/2 and spin-1 Ising versions. Transition probabilities chosen for the pr esent study satisfy the condition of detailed balancing and is a funct ion of spin exchange jump frequencies and spin variables. Energetics o f electron hopping process is obtained from the Ising Hamiltonian unde r molecular field approximation and incorporated into the spin exchang e frequencies. The apparent diffusion coefficient that emerges along w ith the transport equation reflects the dynamics of electron propagati on in the films. The importance of blocking factor and potential indep endent terms in the apparent diffusion coefficient expression overlook ed in hitherto known phenomenological approaches is emphasized.