Étude Théorique des Propriétés Électroniques et Électrochimiques de la Polyaniline

The electronic band structures of various neutral and charged forms of polyaniline are discussed. The MNDO semiempirical technique is used to determine the polyaniline chain geometries. Band‐structure calculations, based on those geometries, are then performed with the VEH method. We obtain theoretical estimates of ionization potentials, bandgaps, electron affinities and redox potentials which are in good agreement with experiment. We discuss in detail the electrochemical properties of polyaniline in aqueous media and the structural evolution of the polymeric chains upon oxydation and reduction. We propose a model for the electrochemical properties of polyaniline which is in excellent agreement with experimental data and theoretical predictions.