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

Zhugayevych, Andriy; Lin, Kun-Han; Andrienko, Denis

doi:10.1063/5.0155488

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

Journal Article · Mon Jul 10 00:00:00 EDT 2023 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0155488· OSTI ID:2422544

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Max Planck Institute for Polymer Research, Mainz (Germany)

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.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States). Center for Integrated Nanotechnologies (CINT)

Sponsoring Organization:: German Research Foundation (DFG); USDOE Office of Science (SC)

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 2422544

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 2 Vol. 159; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Amorphous solids
Charge transport
Chemistry
Coarse-grain model
Electronic structure
Frontier molecular orbitals
Localized states
Multiscale methods
Organic semiconductors
Organic solar cells
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Thermal fluctuations

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

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