A theoretical description of charge reorganization energies in molecular organic P‐type semiconductors

Charge transport properties of materials composed of small organic molecules are important for numerous optoelectronic applications. A material's ability to transport charges is considerably influenced by the charge reorganization energies of the composing molecules. Hence, predictions about charge‐transport properties of organic materials deserve reliable statements about these charge reorganization energies. However, using density functional theory which is mostly used for the predictions, the computed reorganization energies depend strongly on the chosen functional. To gain insight, a benchmark of various density functionals for the accurate calculation of charge reorganization energies is presented. A correlation between the charge reorganization energies and the ionization potentials is found which suggests applying IP‐tuning to obtain reliable values for charge reorganization energies. According to benchmark investigations with IP‐EOM‐CCSD single‐point calculations, the tuned functionals provide indeed more reliable charge reorganization energies. Among the standard functionals, ωB97X‐D and SOGGA11X yield accurate charge reorganization energies in comparison with IP‐EOM‐CCSD values. © 2016 Wiley Periodicals, Inc.