Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

On the Question of the Total Energy in the Fermi–Löwdin Orbital Self-Interaction Correction Method

Journal Article · · Journal of Chemical Theory and Computation
 [1];  [2];  [2];  [3];  [3];  [2]
  1. Central Michigan Univ., Mount Pleasant, MI (United States); Central Michigan University
  2. Central Michigan Univ., Mount Pleasant, MI (United States)
  3. Univ. of Texas at El Paso, TX (United States)
+ Show Author Affiliations
The Fermi-Löwdin orbital self-interaction correction (FLOSIC) formalism is a novel method for implementing the Perdew-Zunger self-interaction correction (PZ-SIC) in density functional theory calculations. In this paper we consider how the use of Fermi orbitals affects total energies and other calculated properties compared to a standard approach to PZ-SIC that utilizes the localization equation conditions. Here, we directly compare the results of the two methods using identical basis sets and numerical techniques in calculations for isolated atoms up to Kr and for a large test set of molecules. We find differences in total energies that increase with increasing atomic number and show that these differences can be traced to a less negative SIC correction for the 1s orbital in FLOSIC. Importantly, energies for highest occupied orbitals and molecular atomization energies are nearly identical in the two methods.
Research Organization:
Central Michigan Univ., Mount Pleasant, MI (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0001330; SC0018331
OSTI ID:
1781804
Alternate ID(s):
OSTI ID: 1539142
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 8 Vol. 14; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (34)

Self-Interaction Corrections Within the Fermi-Orbital-Based Formalism book July 2015
Complex Orbitals, Multiple Local Minima, and Symmetry Breaking in Perdew–Zunger Self-Interaction Corrected Density Functional Theory Calculations journal June 2016
Symmetry Breaking within Fermi–Löwdin Orbital Self-Interaction Corrected Density Functional Theory journal November 2017
Multiconfiguration Pair-Density Functional Theory Is Free From Delocalization Error journal November 2017
On the Non‐Orthogonality Problem Connected with the Use of Atomic Wave Functions in the Theory of Molecules and Crystals journal March 1950
An efficient method for calculating maxima of homogeneous functions of orthogonal matrices: Applications to localized occupied orbitals journal November 2004
Effect of the Perdew–Zunger self-interaction correction on the thermochemical performance of approximate density functionals journal January 2004
Tests of functionals for systems with fractional electron number journal April 2007
On the relation between orbital-localization and self-interaction errors in the density functional theory treatment of organic semiconductors journal March 2011
Density‐functional theory with self‐interaction correction: Application to the lithium molecule a) journal March 1985
Localized and canonical atomic orbitals in self‐interaction corrected local density functional approximation journal February 1988
Gaussian‐2 theory for molecular energies of first‐ and second‐row compounds journal June 1991
The effect of the Perdew-Zunger self-interaction correction to density functionals on the energetics of small molecules journal September 2012
Communication: Self-interaction correction with unitary invariance in density functional theory journal March 2014
Fermi orbital derivatives in self-interaction corrected density functional theory: Applications to closed shell atoms journal February 2015
Fermi orbital self-interaction corrected electronic structure of molecules beyond local density approximation journal December 2015
Self-interaction corrections applied to Mg-porphyrin, C 60 , and pentacene molecules journal April 2016
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
Communication: Recovering the flat-plane condition in electronic structure theory at semi-local DFT cost journal November 2017
Comparison of self-interaction-corrections for metal clusters journal February 2002
Localized orbital scaling correction for systematic elimination of delocalization error in density functional approximations journal September 2017
Critical assessment of the self-interaction-corrected–local-density-functional method and its algorithmic implementation journal March 1997
Optimization of Gaussian basis sets for density-functional calculations journal October 1999
Importance of complex orbitals in calculating the self-interaction-corrected ground state of atoms journal November 2011
Using complex degrees of freedom in the Kohn-Sham self-interaction correction journal June 2012
Full self-consistency in the Fermi-orbital self-interaction correction journal May 2017
Proof that ∂ E ∂ n i = ε in density-functional theory journal December 1978
Self-interaction correction to density-functional approximations for many-electron systems journal May 1981
Variational mesh for quantum-mechanical simulations journal April 1990
Accurate forces in a local-orbital approach to the local-density approximation journal August 1990
Accurate and simple analytic representation of the electron-gas correlation energy journal June 1992
Koopmans’ condition for density-functional theory journal September 2010
One- and many-electron self-interaction error in local and global hybrid functionals journal April 2016
The Role of Self-Interaction Corrections, Vibrations, and Spin-Orbit in Determining the Ground Spin State in a Simple Heme journal October 2017

Cited By (7)

Analytic atomic gradients in the fermi-löwdin orbital self-interaction correction: Analytic Atomic Gradients in the Fermi-Löwdin Orbital Self-Interaction Correction journal December 2018
Importance of self-interaction-error removal in density functional calculations on water cluster anions journal January 2020
Fermi-Löwdin orbital self-interaction correction to magnetic exchange couplings journal October 2018
Non-empirical, low-cost recovery of exact conditions with model-Hamiltonian inspired expressions in jmDFT journal April 2019
The effect of self-interaction error on electrostatic dipoles calculated using density functional theory journal November 2019
Self-interaction-free electric dipole polarizabilities for atoms and their ions using the Fermi-Löwdin self-interaction correction journal July 2019
Importance of self-interaction-error removal in density functional calculations on water cluster anions text January 2020

Similar Records

Complex Fermi–Löwdin orbital self-interaction correction
Journal Article · Thu Jun 16 20:00:00 EDT 2022 · Journal of Chemical Physics · OSTI ID:1872758
Fermi-Löwdin-orbital self-interaction correction using the optimized-effective-potential method within the Krieger-Li-Iafrate approximation
Journal Article · Sun Apr 11 20:00:00 EDT 2021 · Physical Review A · OSTI ID:1781837
Density Matrix Implementation of the Fermi–Löwdin Orbital Self-Interaction Correction Method
Journal Article · Tue Jan 03 19:00:00 EST 2023 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory · OSTI ID:1925162

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemical calculations
Electrical energy
Energy
Molecules
Quantum mechanics