Polarizabilities from Long-Range Corrected DFT Calculations

Abstract

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.

Refractive indices of organo‐metallic and ‐metalloid compounds: A long‐range corrected DFT study

“…Conversely, when a contribution of the GGA exchange‐correlation in the functional increases, the computed polarizabilities become higher than the experimental values. This tendency is consistent with our previous results for the refractive indices of small organic molecules and polymers …”

“…Among the functionals studied here, LC‐BLYP is again one of the best functional to yield the lowest MSRE (−0.4%), MARE (0.7%), and RMSD (0.013; see Table ). Similar observations have been made earlier for small organic molecules and polymers . Although the lowest MAXRE is seen for LC‐PBE (1.9%), MAXRE for LC‐BLYP (2.0%) is almost the same.…”

“…Their microscopic theory strongly suggests that the Lorentz–Lorenz equation is a very good approximation even for molecular systems. Indeed, the Lorentz–Lorenz equation yields predictions often in excellent agreement with experiments, when both the polarizability and the density are estimated accurately …”

“…Since the LC‐DFT describes better excitation properties, it may also represent better polarizability. Indeed, we have numerically proven that both the LC‐BLYP and CAM‐B3LYP allow us to evaluate the refractive index of small organic molecules and polymers accurately . Thus, it is interesting to investigate whether the LC‐DFT evaluates refractive indices of metal‐ and metalloid‐containing compounds with a similar accuracy.…”

How accurate are static polarizability predictions from density functional theory? An assessment over 132 species at equilibrium geometry

“…ting density functionals to, or for assessing their performance. Past assessments 21,22 have often utilized experimental values, which may contain nuclear quantum effects that no accurate electronic structure method should reproduce within the Born-Oppenheimer approximation. Some studies 23,24 also appear to suggest that many experimental polarizabilities may contain substantial errors, making a comparison to benchmark wave function theories necessary for a truly fair assessment of the accuracy of polarizability predictions from DFAs.…”