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 Å 3, 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.