Polarizabilities from Long-Range Corrected DFT Calculations

The long-range corrected DFT functionals, LC-BLYP, LC-PBE and CAM-B3LYP with the augmented Dunning-type triple-ζ basis sets represent dynamical polarizabilities at λ = 589.3 nm of 105 medium-sized organic compounds containing C, H, O, N, S, P, F, Cl, Br and I elements with the root mean squared deviations (RMSD) of about 0.34, 0.35, and 0.42 Å3, respectively. These errors do not change appreciably when the augmented double-ζ basis sets are used. The functionals with 100% of Hartree–Fock (HF) exchange at long-range perform best for aromatic compounds and the CAM-B3LYP or B3LYP functionals for fully saturated compounds. The degrees of HF exchange in mid- and long-range affect strongly the shape and location of the distributions of absolute errors in polarizability, P(Δα). The differences between functionals belonging to the BLYP and PBE families, and having the same degree of HF exchange, have much smaller effect on the P(Δα) distributions.