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

Abstract

Self-interaction (SI) error, which results when exchange-correlation contributions to the total energy are approximated, limits the reliability of many density functional approximations. The Perdew-Zunger SI correction (PZSIC), when applied in conjunction with the local spin density approximation (LSDA), improves the description of many properties, but overall, this improvement is limited. Here we propose a modification to PZSIC that uses an iso-orbital indicator to identify regions where local SI corrections should be applied. Using this local-scaling SIC (LSIC) approach with LSDA, we analyze predictions for a wide range of properties including, for atoms, total energies, ionization potentials, and electron affinities, and for molecules, atomization energies, dissociation energy curves, reaction energies, and reaction barrier heights. LSIC preserves the results of PZSIC-LSDA for properties where it is successful and provides dramatic improvements for many of the other properties studied. Atomization energies calculated using LSIC are better than those of the Perdew, Burke, and Ernzerhof (PBE) generalized gradient approximation (GGA) and close to those obtained with the Strongly Constrained and Appropriately Normed (SCAN) meta-GGA. LSIC also restores the uniform gas limit for the exchange energy that is lost in PZSIC-LSDA. Further performance improvements may be obtained by an appropriate combination or modification of the local scaling factor and the particular density functional approximation.

12 pages, 6 figures, to be published in Journal of Chemical Physics

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Cited by in corpus (9)

• Predictive Power of the Exact Constraints and Appropriate Norms in Density Functional Theory
• Importance of self-interaction-error removal in density functional calculations on water cluster anions
• 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
• Improvements in the orbitalwise scaling down of Perdew-Zunger self-interaction correction in many-electron regions
• Self-Interaction Correction in Water-Ion Clusters
• Study of self-interaction-errors in barrier heights using locally scaled and Perdew-Zunger self-interaction methods
• Exploring and enhancing the accuracy of interior-scaled Perdew-Zunger self-interaction correction
• Static dipole polarizabilities of polyacenes using self-interaction-corrected density functional approximations
• Study of Self-Interaction Errors in Density Functional Calculations of Magnetic Exchange Coupling Constants Using Three Self-Interaction Correction Methods