DFT modeling of polyaniline: a computational investigation into the structure and band gap of polyaniline
- 1 February 2022
- journal article
- research article
- Published by Canadian Science Publishing in Canadian Journal of Chemistry
- Vol. 100 (2), 162-167
- https://doi.org/10.1139/cjc-2021-0169
Abstract
The band gaps of three forms of polyaniline (PANI) are calculated using the DFT method with the B3LYP functional and SV(P) basis set. This marks the first time that the band gap for this polymer has been calculated using this DFT method. The calculations include an investigation of the effect of varying the benzoid-quinoid structural units, the effect of increasing oligomer length and the inclusion of Michael’s addition structures which could be residual in the polymer depending on the chosen synthetic method. All results were compared to the experimentally determined band gap of 1.5 eV as typically reported in the literature. A commonly used structural motif of alternating benzoid-quinoid units and a ratio of 0.5:0.5 benzoid: quinoid resulted in a computed band gap of 1.9 eV. Inclusion of one extra quinoid unit gave rise to a band gap of 1.3 eV. Incorporation of a Michael’s addition structure was found to dominate the band gap calculation, yielding a localized LUMO and a band gap of 1.3 eV that was insensitive to the polymer chain length and composition.Keywords
This publication has 30 references indexed in Scilit:
- Electronic Properties of Vinylene-Linked Heterocyclic Conducting Polymers: Predictive Design and Rational Guidance from DFT CalculationsThe Journal of Physical Chemistry C, 2011
- Spectroscopic Characterization of Oligoaniline Microspheres Obtained by an Aniline−Persulfate ApproachThe Journal of Physical Chemistry B, 2011
- Polyaniline as a hole injection layer on organic photovoltaic cellsSolar Energy Materials and Solar Cells, 2010
- Doping of Polyaniline by Acid−Base Chemistry: Density Functional Calculations with Periodic Boundary ConditionsJournal of the American Chemical Society, 2005
- Bandgap calculations for conjugated polymersSynthetic Metals, 2004
- Calculations of Band Gaps in Polyaniline from Theoretical Studies of OligomersThe Journal of Physical Chemistry B, 2000
- Polyaniline: A polymer with many interesting intrinsic redox statesProgress in Polymer Science, 1998
- Electrochemical Growth of Polyaniline in Porous Sol−Gel FilmsChemistry of Materials, 1996
- Fully optimized contracted Gaussian basis sets for atoms Li to KrThe Journal of Chemical Physics, 1992
- X-ray structure of polyanilineMacromolecules, 1991