Computational prediction for oxidation and reduction potentials of organic molecules used in organic light-emitting diodes

Abstract

Abstract The performance of organic electrical devices is highly dependent on the oxidation potential (EOX) and the reduction potential (ERED) of the used materials. To develop a generalized method for predicting the redox potentials of organic semiconductors, we assess the performance of 13 density functionals (i.e., PBE, BLYP, B3LYP, PBE0, M06, M062X, M06HF, CAM-B3LYP, ωB97, ωB97X, ωB97XD, LC-ωPBE* and B2PLYP) for estimating the EOX and ERED of 50 compounds used in organic light-emitting diodes on the basis of thermodynamic cycles for electron transfer. In comparison with the experimental data measured by cyclic voltammetry, the combination of PBE0 with def2TZVP basis set and B3LYP or M06 with 6–311++G (d, p) basis set is found to give reliable Eox and Ered with a mean absolute error of 0.05 V and 0.08 V, respectively. The correlations between the theoretical frontier orbital energies and the measured redox potentials are also investigated.