Comparative study of unscreened and screened molecular static linear polarizability in the Hartree-Fock, hybrid-density functional, and density functional models

TL;DR

This study compares sum-over-states and finite-field methods for calculating molecular polarizabilities across Hartree-Fock, B3LYP, and PBE models, revealing systematic overestimations and proposing a correction scheme.

Contribution

It provides a comprehensive comparison of polarizability calculation methods and introduces a simple correction scheme to improve SOS estimates based on observed trends.

Findings

SOS overestimates B3LYP and PBE polarizabilities

Hartree-Fock predicts smaller polarizabilities than DFT models

Proposed correction scheme improves SOS estimates

Abstract

The sum-over-states (SOS) polarizabilities are calculated within the approximate independent electron theories such as the Hartree-Fock approximation and density functional models using the eigenvalues and orbitals obtained from the self-consistent solution of single-particle equations. The SOS polarizabilities are then compared with those calculated using the finite-field method within three widely used single particle models: (1) the Hartree-Fock (HF) method, (2) the three parameter hybrid generalized gradient approximation (B3LYP), and (3) the parameter free generalized gradient approximation due to Perdew-Burke-Ernzerhof (PBE). The comparison is carried out for polarizabilities of 142 molecules calculated using the 6-311++G(d,p) orbital basis at the geometries optimized at the B3LYP/6-311G** level. The results show that the SOS method almost always overestimate the FF polarizabilities in the PBE and B3LYP models. This trend is reversed in the HF method however exception to the trend do exist. The mean absolute errors (MAE) in the screened (FF) and unscreened (SOS) polarizability are 0.78 \AA$^3$ for the HF method, 1.87 \AA$^3$ for the B3LYP, and 3.44 \AA$^3$ for the PBE-GGA. The Hartree-Fock approximation predicts finite-field polarizabilities that are smaller than those predicted by the PBE and B3LYP models. Finally, a simple scheme is devised to obtain FF quality estimate of polarizability from those obtained using the SOS method by exploiting the observed trends.