Assessment of density functional methods for exciton binding energies and related optoelectronic properties

Abstract

The exciton binding energy, the energy required to dissociate an excited electron–hole pair into free charge carriers, is one of the key factors to the optoelectronic performance of organic materials. However, it remains unclear whether modern quantum-mechanical calculations, mostly based on Kohn–Sham density functional theory (KS-DFT) and time-dependent density functional theory (TDDFT), are reliably accurate for exciton binding energies. In this study, the exciton binding energies and related optoelectronic properties (e.g., the ionization potentials, electron affinities, fundamental gaps, and optical gaps) of 121 small- to medium-sized molecules are calculated using KS-DFT and TDDFT with various density functionals. Our KS-DFT and TDDFT results are compared with those calculated using highly accurate CCSD and EOM-CCSD methods, respectively. The ωB97, ωB97X, and ωB97X-D functionals are shown to generally outperform (with a mean absolute error of 0.36 eV) other functionals for the properties investigated.