Electronic Structure and Conformational Properties of Polybenzimidazole-Based Ionenes—A Density Functional Theory Investigation

[Image: see text] Polybenzimidazole-based ionenes are explored for use in both alkaline anion-exchange membrane fuel cells and alkaline polymer electrolyzers. Poly-(hexamethyl-p-terphenylbenzimidazolium) (HMT-PMBI), the material of interest in this article, is exceptionally hydroxide-stable and water-insoluble. The impact of the degree of methylation on conformations and electronic structure properties of HMT-PMBI oligomers, from the monomer to the pentamer, is studied with density functional theory calculations. Optimization studies are presented for both the gas phase and in the presence of implicit water. In addition, time-dependent density functional theory is employed to generate the UV–vis absorption spectra of the studied systems. Results are insightful for experimentalists and theorists investigating the impact of synthetic and environmental conditions on the conformation and electronic properties of polybenzimidazole-based membranes.