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

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.

Automated summary

By neglecting intramolecular charge transfer, existing charge transport models of molecular solids fail to account for materials with quasi-degenerate spatially separated frontier orbitals. Through analyzing the electronic structure of a prototypical non-fullerene acceptor, ITIC-4F, it is found that the electron is localized on one of the acceptor blocks, indicating the necessity of considering intramolecular transfer in charge transport modeling. Failure to do so can lead to significant underestimation of charge carrier mobility for acceptor-donor-acceptor (A-D-A) molecules.