Visualizations of charge transfer for the model of poly(3,4-alkylenedioxythiophene)s in neutral and various oxidation states

Abstract

The charge transfer mechanisms of the poly(3,4-alkylenedioxythiophene)s model in neutral and various oxidation states are theoretically investigated, which is stimulated by the recent experimental reports [C. Lin, et al., J. Am. Chem. Soc. 2011, 133, 11339.]. Due to the difference of charge distribution on different units at various oxidation states, the bond lengths of inter-units are significantly different. The properties of excitons and polarons in poly(3,4-alkylenedioxythiophene)s model in neutral and various oxidation states were revealed by quantum chemical calculations. In particular, simultaneous use of different correlation plots in atomic site representation and transition densities in real space representation reveals the electronic structure and spatial localization of the elementary excitations. Theoretical results state that the charge transfer mechanisms for neutral and oxidation states are significantly different. The theoretical results promote deeper understanding for the structural, optical and electronic properties of poly(3,4-alkylenedioxythiophene)s model, and will offer crucial hints for the rational design of novel transparent conductive poly(3,4-alkylenedioxythiophene)s and relative polymers.