The effect of self-interaction error on electrostatic dipoles calculated using density functional theory

Johnson, Alexander I.; Withanage, Kushantha P.  K.; Sharkas, Kamal; Yamamoto, Yoh; Baruah, Tunna; Zope, Rajendra R.; Peralta, Juan E.; Jackson, Koblar A.

doi:10.1063/1.5125205

Title: The effect of self-interaction error on electrostatic dipoles calculated using density functional theory

Journal Article · Mon Nov 04 00:00:00 EST 2019 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5125205· OSTI ID:1596360

Johnson, Alexander I. ^[1]; Withanage, Kushantha P. K. ^[1]; Sharkas, Kamal ^[1];

^[2]; Baruah, Tunna ^[2];

^[2];

^[1];

^[1]

Central Michigan Univ., Mount Pleasant, MI (United States)
Univ. of Texas at El Paso, TX (United States)

Spurious electron self-interaction in density functional approximations (DFAs) can lead to inaccurate predictions of charge transfer in heteronuclear molecules that manifest as errors in calculated electrostatic dipoles. Here we show the magnitude of these errors on dipoles computed for a diverse set of 47 molecules taken from the recent benchmark study of Hait and Head-Gordon. We compare results of Perdew-Wang local spin density approximation (PW92), Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA), and strongly constrained and appropriatedly normed (SCAN) meta-GGA dipole calculations, along with those of their respective self-interaction-corrected (SIC) counterparts, to reference values from accurate wave function-based methods. The SIC calculations were carried out using the Fermi-Löwdin orbital (FLO-SIC) approach. We find that correcting for self-interaction generally increases the degree of charge transfer, thereby increasing the size of calculated dipole moments. The FLO-SIC-PW92 and FLO-SIC-PBE dipoles are in better agreement with reference values than their uncorrected DFA counterparts, particularly for strongly ionic molecules where significant improvement is seen. Applying FLO-SIC to SCAN does not improve dipole values overall. In addition, we show that removing self-interaction improves the description of the dipole for stretched-bond geometries and recovers the physically correct separated atom limit of zero dipole. Finally, we find that the best agreement between the FLO-SIC-DFA and reference dipoles occurs when the molecular geometries are optimized using the FLO-SIC-DFA.

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Research Organization:: Univ. of Texas at El Paso, TX (United States); Central Michigan Univ., Mount Pleasant, MI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0018331

OSTI ID:: 1596360

Alternate ID(s):: OSTI ID: 1573086

Journal Information:: Journal of Chemical Physics, Vol. 151, Issue 17; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 28 works

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Importance of self-interaction-error removal in density functional calculations on water cluster anions Vargas, Jorge; Ufondu, Peter; Baruah, Tunna Physical Chemistry Chemical Physics, Vol. 22, Issue 7 https://doi.org/10.1039/c9cp06106a	journal	January 2020
A step in the direction of resolving the paradox of Perdew-Zunger self-interaction correction Zope, Rajendra R.; Yamamoto, Yoh; Diaz, Carlos M. The Journal of Chemical Physics, Vol. 151, Issue 21 https://doi.org/10.1063/1.5129533	journal	December 2019
Importance of self-interaction-error removal in density functional calculations on water cluster anions Vargas, Jorge; Ufondu, Peter; Baruah, Tunna arXiv https://doi.org/10.48550/arxiv.2002.03481	text	January 2020
A step in the direction of resolving the paradox of Perdew–Zunger self-interaction correction. II. Gauge consistency of the energy density at three levels of approximation Bhattarai, Puskar; Wagle, Kamal; Shahi, Chandra The Journal of Chemical Physics, Vol. 152, Issue 21 https://doi.org/10.1063/5.0010375	journal	June 2020
Self-Interaction Correction in Water-Ion Clusters Wagle, Kamal; Santra, Biswajit; Bhattarai, Puskar arXiv https://doi.org/10.48550/arxiv.2012.13469	text	January 2020

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