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 »
- Authors:
-
[2];
[2];
[1];
[1]
- Central Michigan Univ., Mount Pleasant, MI (United States)
- 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. doi: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 referenced in this record:
Proof that in density-functional theory
journal, December 1978
- Janak, J. F.
- Physical Review B, Vol. 18, Issue 12
Accurate forces in a local-orbital approach to the local-density approximation
journal, August 1990
- Jackson, Koblar; Pederson, Mark R.
- Physical Review B, Vol. 42, Issue 6
Self-consistent self-interaction corrected density functional theory calculations for atoms using Fermi-Löwdin orbitals: Optimized Fermi-orbital descriptors for Li–Kr
journal, October 2017
- Kao, Der-you; Withanage, Kushantha; Hahn, Torsten
- The Journal of Chemical Physics, Vol. 147, Issue 16
On the Question of the Total Energy in the Fermi–Löwdin Orbital Self-Interaction Correction Method
journal, June 2018
- Withanage, Kushantha P. K.; Trepte, Kai; Peralta, Juan E.
- Journal of Chemical Theory and Computation, Vol. 14, Issue 8
Spurious fractional charge on dissociated atoms: Pervasive and resilient self-interaction error of common density functionals
journal, November 2006
- Ruzsinszky, Adrienn; Perdew, John P.; Csonka, Gábor I.
- The Journal of Chemical Physics, Vol. 125, Issue 19
Scaling down the Perdew-Zunger self-interaction correction in many-electron regions
journal, March 2006
- Vydrov, Oleg A.; Scuseria, Gustavo E.; Perdew, John P.
- The Journal of Chemical Physics, Vol. 124, Issue 9
Self-interaction error of local density functionals for alkali–halide dissociation
journal, April 2006
- Dutoi, Anthony D.; Head-Gordon, Martin
- Chemical Physics Letters, Vol. 422, Issue 1-3
Variational mesh for quantum-mechanical simulations
journal, April 1990
- Pederson, Mark R.; Jackson, Koblar A.
- Physical Review B, Vol. 41, Issue 11
A second-order perturbative correction to the coupled-cluster singles and doubles method: CCSD(2)
journal, August 2001
- Gwaltney, Steven R.; Head-Gordon, Martin
- The Journal of Chemical Physics, Vol. 115, Issue 5
Molpro: a general-purpose quantum chemistry program package: Molpro
journal, July 2011
- Werner, Hans-Joachim; Knowles, Peter J.; Knizia, Gerald
- Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2
Self-interaction correction to density-functional approximations for many-electron systems
journal, May 1981
- Perdew, J. P.; Zunger, Alex
- Physical Review B, Vol. 23, Issue 10, p. 5048-5079
Fermi orbital derivatives in self-interaction corrected density functional theory: Applications to closed shell atoms
journal, February 2015
- Pederson, Mark R.
- The Journal of Chemical Physics, Vol. 142, Issue 6
Fermi-Löwdin orbital self-interaction correction using the strongly constrained and appropriately normed meta-GGA functional
journal, October 2019
- Yamamoto, Yoh; Diaz, Carlos M.; Basurto, Luis
- The Journal of Chemical Physics, Vol. 151, Issue 15
Full self-consistency in the Fermi-orbital self-interaction correction
journal, May 2017
- Yang, Zeng-hui; Pederson, Mark R.; Perdew, John P.
- Physical Review A, Vol. 95, Issue 5
Correct dissociation behavior of radical ions such as H2+ in density functional calculations
journal, January 2001
- Chermette, H.; Ciofini, I.; Mariotti, F.
- The Journal of Chemical Physics, Vol. 114, Issue 4
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
The multi-state CASPT2 method
journal, May 1998
- Finley, James; Malmqvist, Per-Åke; Roos, Björn O.
- Chemical Physics Letters, Vol. 288, Issue 2-4
How Accurate Is Density Functional Theory at Predicting Dipole Moments? An Assessment Using a New Database of 200 Benchmark Values
journal, March 2018
- Hait, Diptarka; Head-Gordon, Martin
- Journal of Chemical Theory and Computation, Vol. 14, Issue 4
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions
journal, May 1992
- Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J.
- The Journal of Chemical Physics, Vol. 96, Issue 9
Stretched or noded orbital densities and self-interaction correction in density functional theory
journal, May 2019
- Shahi, Chandra; Bhattarai, Puskar; Wagle, Kamal
- The Journal of Chemical Physics, Vol. 150, Issue 17
A simple method to selectively scale down the self-interaction correction
journal, May 2006
- Vydrov, Oleg A.; Scuseria, Gustavo E.
- The Journal of Chemical Physics, Vol. 124, Issue 19
XXXIV. Notes on the molecular orbital treatment of the hydrogen molecule
journal, April 1949
- Coulson, C. A.; Fischer, I.
- The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science, Vol. 40, Issue 303
Optimization of Gaussian basis sets for density-functional calculations
journal, October 1999
- Porezag, Dirk; Pederson, Mark R.
- Physical Review A, Vol. 60, Issue 4
Basis set dependence of atomic spin populations
journal, July 2010
- Philips, Jordan J.; Hudspeth, Mathew A.; Browne, Philip M.
- Chemical Physics Letters, Vol. 495, Issue 1-3
Fermi-Löwdin orbital self-interaction corrected density functional theory: Ionization potentials and enthalpies of formation: Fermi-Löwdin Orbital Self-interaction Corrected Density Functional Theory: Ionization Potentials and Enthalpies of Formation
journal, October 2018
- Schwalbe, Sebastian; Hahn, Torsten; Liebing, Simon
- Journal of Computational Chemistry, Vol. 39, Issue 29
Well-behaved versus ill-behaved density functionals for single bond dissociation: Separating success from disaster functional by functional for stretched H 2
journal, March 2019
- Hait, Diptarka; Rettig, Adam; Head-Gordon, Martin
- The Journal of Chemical Physics, Vol. 150, Issue 9
Importance of complex orbitals in calculating the self-interaction-corrected ground state of atoms
journal, November 2011
- Klüpfel, Simon; Klüpfel, Peter; Jónsson, Hannes
- Physical Review A, Vol. 84, Issue 5
Accurate and simple analytic representation of the electron-gas correlation energy
journal, June 1992
- Perdew, John P.; Wang, Yue
- Physical Review B, Vol. 45, Issue 23, p. 13244-13249
Interpretation and Automatic Generation of Fermi‐Orbital Descriptors
journal, September 2019
- Schwalbe, Sebastian; Trepte, Kai; Fiedler, Lenz
- Journal of Computational Chemistry, Vol. 40, Issue 32
A posteriori corrections to systematic failures of standard density functionals: The dissociation of two-center three-electron systems
journal, December 2001
- Chermette, H.; Ciofini, I.; Mariotti, F.
- The Journal of Chemical Physics, Vol. 115, Issue 24
Perdew-Zunger self-interaction correction: How wrong for uniform densities and large- Z atoms?
journal, May 2019
- Santra, Biswajit; Perdew, John P.
- The Journal of Chemical Physics, Vol. 150, Issue 17
Strongly Constrained and Appropriately Normed Semilocal Density Functional
journal, July 2015
- Sun, Jianwei; Ruzsinszky, Adrienn; Perdew, John P.
- Physical Review Letters, Vol. 115, Issue 3
Communication: Self-interaction correction with unitary invariance in density functional theory
journal, March 2014
- Pederson, Mark R.; Ruzsinszky, Adrienn; Perdew, John P.
- The Journal of Chemical Physics, Vol. 140, Issue 12
Inhomogeneous Electron Gas
journal, November 1964
- Hohenberg, P.; Kohn, W.
- Physical Review, Vol. 136, Issue 3B, p. B864-B871
Inhomogeneous Electron Gas
journal, March 1973
- Rajagopal, A. K.; Callaway, J.
- Physical Review B, Vol. 7, Issue 5
Importance of complex orbitals in calculating the self-interaction-corrected ground state of atoms
text, January 2013
- Klüpfel, Simon; Klüpfel, Peter; Jonsson, Hannes
- arXiv
Strongly Constrained and Appropriately Normed Semilocal Density Functional
preprint, January 2015
- Sun, Jianwei; Ruzsinszky, Adrienn; Perdew, John P.
- arXiv
Full self-consistency in Fermi-orbital self-interaction correction
text, January 2017
- Yang, Zeng-hui; Pederson, Mark R.; Perdew, John P.
- arXiv
Well-behaved versus ill-behaved density functionals for single bond dissociation: Separating success from disaster functional by functional for stretched H$_2$
text, January 2018
- Hait, Diptarka; Rettig, Adam; Head-Gordon, Martin
- arXiv
Works referencing / citing this record:
Importance of self-interaction-error removal in density functional calculations on water cluster anions
journal, January 2020
- Vargas, Jorge; Ufondu, Peter; Baruah, Tunna
- Physical Chemistry Chemical Physics, Vol. 22, Issue 7
A step in the direction of resolving the paradox of Perdew-Zunger self-interaction correction
journal, December 2019
- Zope, Rajendra R.; Yamamoto, Yoh; Diaz, Carlos M.
- The Journal of Chemical Physics, Vol. 151, Issue 21
Importance of self-interaction-error removal in density functional calculations on water cluster anions
text, January 2020
- Vargas, Jorge; Ufondu, Peter; Baruah, Tunna
- arXiv