Exploring polaron formation in PEDOT oligomers through Advanced DFT analysis

Abstract

In this short communication, we delve into the intriguing electronic structure of Poly(3,4-ethylenedioxythiophene) (PEDOT) to explore the formation of polarons. Through density functional theory approaches, the formation of polarons in PEDOT oligomers was explored, shedding light on their unique characteristics. The ωB97XD/6-311G(d,p) level of theory was adopted to investigate the oxidized states q = 0, q = 1, and q = 2 to understand their geometry optimization in different oxidation states. By calculating vibrational mode spectra, molecular orbital energies, Wiberg bond indices, and formal atomic charges, valuable insights into the intricate details of polaron formation were obtained. Our proposal of using Natural Bond Orbitals analysis, resulted in the conclusion that Wiberg Bond Indexes are a robust alternative for characterizing non-covalent interactions, providing a localized description of electron pairs and facilitating the interpretation of complex quantum mechanical electronic structures.