Issue 34, 2021

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

Abstract

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.

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

Supplementary files

Article information

Article type
Paper
Submitted
16 Dec 2020
Accepted
02 Aug 2021
First published
10 Aug 2021

Phys. Chem. Chem. Phys., 2021,23, 18678-18685

Author version available

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

S. Akter, J. A. Vargas, K. Sharkas, J. E. Peralta, K. A. Jackson, T. Baruah and R. R. Zope, Phys. Chem. Chem. Phys., 2021, 23, 18678 DOI: 10.1039/D0CP06512A

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