Electronic coarse-graining of long conjugated molecules: Case study of non-fullerene acceptors

Andriy Zhugayevych, Kun-Han Lin, Denis Andrienko

Research output: Contribution to journalArticlepeer-review


By considering only one electronic state per molecule, charge transport models of molecular solids neglect intramolecular charge transfer. This approximation excludes materials with quasi-degenerate spatially separated frontier orbitals, such as non-fullerene acceptors (NFAs) and symmetric thermally activated delayed fluorescence emitters. By analyzing the electronic structure of room-temperature molecular conformers of a prototypical NFA, ITIC-4F, we conclude that the electron is localized on one of the two acceptor blocks with the mean intramolecular transfer integral of 120 meV, which is comparable with intermolecular couplings. Therefore, the minimal basis for acceptor–donor–acceptor (A–D–A) molecules consists of two molecular orbitals localized on the acceptor blocks. This basis is robust even with respect to geometry distortions in an amorphous solid, in contrast to the basis of two lowest unoccupied canonical molecular orbitals withstanding only thermal fluctuations in a crystal. The charge carrier mobility can be underestimated by a factor of two when using single site approximation for A–D–A molecules in their typical crystalline packings.
Original languageEnglish (US)
JournalThe Journal of chemical physics
Issue number2
StatePublished - Jul 10 2023
Externally publishedYes

Bibliographical note

KAUST Repository Item: Exported on 2023-07-18
Acknowledgements: We thank Wenlan Liu, Mukunda Mandal, and Naomi Kinaret for the fruitful discussions. This work was performed, in part, at the Center for Integrated Nanotechnologies, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Los Alamos National Laboratory (Contract No. 89233218CNA000001) and Sandia National Laboratories (Contract No. DE-NA-0003525). D.A. acknowledges the KAUST PSE Division for hosting his sabbatical in the framework of the Division’s Visiting Faculty program. D.A. acknowledges funding by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) for financial support through the collaborative research centers TRR 146, SPP 2196, and Grant No. 460766640.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.

ASJC Scopus subject areas

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry


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