Effect of chalcogen atoms on the electronic band gaps of donor-acceptor-donor type semiconducting polymers: a systematic DFT investigation

Ozkilinc O., KAYI H.

JOURNAL OF MOLECULAR MODELING, vol.25, no.6, 2019 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 25 Issue: 6
  • Publication Date: 2019
  • Doi Number: 10.1007/s00894-019-4043-2
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Keywords: Electronic band gap, Donor-acceptor-donor, Conjugated polymers, Semiconducting polymers, Chalcogen atoms, Density functional theory, MOLECULAR-ORBITAL METHODS, GAUSSIAN-TYPE BASIS, AB-INITIO, CONJUGATED POLYMERS, CONTINUUM, ENERGY, DESIGN, COMPUTATION, POTENTIALS, OLIGOMERS
  • Ankara University Affiliated: Yes


We systematically investigated and compared the electronic band gaps of 16 different donor-acceptor-donor type semiconducting polymer systems that included different chalcogen atoms in their donor and acceptor units. The five-membered heterocyclic rings furan, thiophene, selenophene, and tellurophene were considered as electron donor units, whereas benzochalcogenadiazole groups, i.e., benzoxadiazole, benzothiadiazole, benzoselenadiazole, and benzotelluradiazole, were used as electron acceptor units. Our findings from B3LYP/6-31G(d) and B3LYP/LANL2DZ calculations performed with and without the polarizable continuum model indicated that the size of the chalcogen atom used as a heteroatom in the donor units plays a more important role than the size of the chalcogen atom in the benzochalcogenadiazole acceptor unit does. On the other hand, our results also suggest that the best way to modify and narrow the electronic band gap is to use heavy chalcogen atoms in both donor and acceptor units.