Improved Prediction of Properties of π-Conjugated Oligomers with Range-Separated Hybrid Density Functionals.

Range-separated hybrid functionals along with global hybrids and pure density functionals have been employed to calculate geometries, ionization energies (IP)s, electron affinities (EA)s, and excitation energies of neutral and oxidized polyenes, thiophene, and furan oligomers. Long-range correction with 100% HF exchange solves the problem of density functional theory with incorrect chain length dependence of IPs and energy gaps. There is a possibility of overcorrection, if the short-range part of the functional with no or low HF exchange is too small. The wB97XD functional with 22% of HF exchange in the short-range and a range-separation parameter of 0.2 seems to be just right for conjugated systems at all chain lengths. The wB97XD functional additionally produces negative orbital energies in very good agreement with IPs and EAs. With correct orbital energies, band gaps correspond to transport gaps (Et) and not to optical gaps (Eg). Et is much larger than Eg in the gas phase, but the difference is significantly smaller in the solid state. The accuracy of the negative orbital energies is good down to about 30 eV so that valence and innervalence PE spectra can be modeled. wB97XD is therefore suitable for calculating band structures of conjugated polymers employing orbital energies.