Large‐Scale Determination of Frontier Orbital Energies of Disordered Small‐Molecule Organic Semiconductors Using Exciplex Emission Spectra

1.0 eV is argued to be larger than the adiabatic value due to spectral redshifts as a result of exciplex diffusion, exciplex-vibron coupling and a Stokes shift. The database is highly redundant, and allows obtaining relative accuracies better than 0.1 eV. Calibration using the frontier orbital energies of well-studied materials leads to precise absolute values, as deduced from a comparison with spectroscopic data. The method is easy and fast, can be readily applied to novel materials, and provides thereby an accurate basis for predictive device simulations.