How well do self-interaction corrections repair the overestimation of static polarizabilities in density functional calculations?

• Published in: Physical chemistry chemical physics : PCCP Vol. 23; no. 34; pp. 18678 - 18685
• Main Authors: Akter, Sharmin, Vargas, Jorge A, Sharkas, Kamal, Peralta, Juan E, Jackson, Koblar A, Baruah, Tunna, Zope, Rajendra R
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 14.09.2021; Royal Society of Chemistry (RSC)
• Subjects: Approximation; Density; Mathematical analysis
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d0cp06512a

We examine the effect of removing self-interaction error (SIE) on the calculation of molecular polarizabilities in the local spin density (LSDA) and generalized gradient approximations (GGA). To this end, we utilize a database of 132 molecules taken from a recent benchmark study [Hait and Head-Gordon, Phys. Chem. Chem. Phys. , 2018, 20 , 19800] to assess the influence of SIE on polarizabilities by comparing results with accurate reference data. Our results confirm that the general overestimation of molecular polarizabilities by these density functional approximations can be attributed to SIE. However, removing SIE using the Perdew-Zunger self-interaction-correction (PZ-SIC) method, implemented using the Fermi-Löwdin Orbital SIC approach, leads to an underestimation of molecular polarizabilities, showing that PZ-SIC overcorrects when combined with LSDA or GGA. Application of a recently proposed locally scaled SIC [Zope, et al. , J. Chem. Phys. , 2019, 151 , 214108] is found to provide more accurate polarizabilities. We attribute this to the ability of the local scaling scheme to selectively correct for SIE in the regions of space where the correction is needed most. This article investigates the role of self-interaction error on the molecular polarizabilities calculated within the local spin density and generalized gradient approximations.