Comparison of self-consistent calculations of the static polarizability of atoms and molecules

Abstract

The static dipole polarizabilities and other ground-state properties of H, H2, He, Na, and Na2 are calculated using five different self-consistent schemes: Hartree–Fock, local spin density approximation, Hartree–Fock plus local density correlation, self-interaction-corrected local spin density approximation, and Hartree–Fock plus self-interaction-corrected local density correlation. The inclusion of the self-interaction corrected local spin density approximation in the Hartree–Fock method improves dramatically the calculated dissociation energies of molecules but has a small effect on the calculated polarizabilities. Correcting the local spin density calculations for self-interaction effects improves the calculated polarizability in the cases where the local spin density results are mediocre, and has only a small effect in the cases where the local spin density values are in reasonable agreement with experiment.

The accurate calculation of dipole moments and dipole polarizabilities using Gaussian‐based density functional methods

“…The fact that electron-correlation is included should mean that the results of LDF calculations will be closer to experiment than those obtained by Hartree-Fock calculations. The work of Moullet and Martins on atoms [5], and Krijn and Feil on the water molecule [6], have shown this to be the case. More recently, Jasien and Fitzgerald [7] performed the first calculations of these properties for a large number of polyatomic molecules.…”

Local Density-Functional Polarizabilities and Hyperpolarizabilities at the Basis-Set Limit

“…It is especially useful in medium and large systems where post-Hartree−Fock methods become prohibitively expensive. But most density-functional determinations of electrical properties are carried out with basis-set expansions whose convergence must be laboriously verified for each new property calculated. − Therefore, in the present work we given multipole moments, static polarizabilities, and hyperpolarizabilities for a few benchmark systems using our unique basis-set-free density-functional code NUMOL. , …”

Polarizability of phthalocyanine based molecular systems: A first-principles electronic structure study

“…An electric field of strength 0.01 V / Å was used in the determination of ␣ ij . As a test of our method, we have determined the polarizability of a number of simple atoms and molecules for which prior computational 13 and/or experimental results 14 are available. Table I.…”