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

Abstract

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 themore » best agreement between the FLO-SIC-DFA and reference dipoles occurs when the molecular geometries are optimized using the FLO-SIC-DFA.« less

Authors:
 [1];  [1];  [1]; ORCiD logo [2];  [2]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Central Michigan Univ., Mount Pleasant, MI (United States)
  2. Univ. of Texas at El Paso, TX (United States)
Publication Date:
Research Org.:
Univ. of Texas at El Paso, TX (United States); Central Michigan Univ., Mount Pleasant, MI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1596360
Alternate Identifier(s):
OSTI ID: 1573086
Grant/Contract Number:  
SC0018331
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 17; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Johnson, Alexander I., Withanage, Kushantha P. K., Sharkas, Kamal, Yamamoto, Yoh, Baruah, Tunna, Zope, Rajendra R., Peralta, Juan E., and Jackson, Koblar A. The effect of self-interaction error on electrostatic dipoles calculated using density functional theory. United States: N. p., 2019. Web. https://doi.org/10.1063/1.5125205.
Johnson, Alexander I., Withanage, Kushantha P. K., Sharkas, Kamal, Yamamoto, Yoh, Baruah, Tunna, Zope, Rajendra R., Peralta, Juan E., & Jackson, Koblar A. The effect of self-interaction error on electrostatic dipoles calculated using density functional theory. United States. https://doi.org/10.1063/1.5125205
Johnson, Alexander I., Withanage, Kushantha P. K., Sharkas, Kamal, Yamamoto, Yoh, Baruah, Tunna, Zope, Rajendra R., Peralta, Juan E., and Jackson, Koblar A. Mon . "The effect of self-interaction error on electrostatic dipoles calculated using density functional theory". United States. https://doi.org/10.1063/1.5125205. https://www.osti.gov/servlets/purl/1596360.
@article{osti_1596360,
title = {The effect of self-interaction error on electrostatic dipoles calculated using density functional theory},
author = {Johnson, Alexander I. and Withanage, Kushantha P. K. and Sharkas, Kamal and Yamamoto, Yoh and Baruah, Tunna and Zope, Rajendra R. and Peralta, Juan E. and Jackson, Koblar A.},
abstractNote = {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.},
doi = {10.1063/1.5125205},
journal = {Journal of Chemical Physics},
number = 17,
volume = 151,
place = {United States},
year = {2019},
month = {11}
}

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    Works referencing / citing this record:

    A step in the direction of resolving the paradox of Perdew-Zunger self-interaction correction
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