A molecular dynamics study of ion migration in a doped electroactive polymer

Simulating the hbox{BF}_{4}^{-} -doped poly(3-octylthiophene) lattice by molecular dynamics results in a structure in which dopant ions intercalate as a sandwich between thiophene rings on adjacent polymer chains. The ions occupy sites in channels parallel to the polymer main chain, which retains a high degree of planarity in contrast to the pristine (undoped) polymer. Even when lattice imperfections are created by expanding the cell, Coulomb forces ensure that the intercalation features containing the dopant channels are largely retained. On applying electric fields in the principal directions of the 'perfect lattice' it is found that the ions migrate most readily along the ion-channel directions (the lattice c axis), leaving the lattice undisturbed. Although higher electric fields cause dopant migration to occur perpendicular to the channel directions they destroy the intercalated lattice. In the reduced-order lattice regions substantial motion of the ions are predicted at a critical value of the lattice parameter.