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Journal of Chemical Physics / Volume 124 / Issue 9 / ARTICLES / Theoretical Methods and Algorithms

J. Chem. Phys. 124, 094108 (2006); http://dx.doi.org/10.1063/1.2176608 (8 pages)

Scaling down the Perdew-Zunger self-interaction correction in many-electron regions

Oleg A. Vydrov1, Gustavo E. Scuseria1, John P. Perdew2, Adrienn Ruzsinszky2, and Gábor I. Csonka3

1Department of Chemistry, Rice University, Houston, Texas 77005
2Department of Physics and Quantum Theory Group, Tulane University, New Orleans, Louisiana 70118
3Department of Inorganic Chemistry, Budapest University of Technology and Economics, H-1521 Budapest, Hungary

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(Received 28 November 2005; accepted 23 January 2006; published online 3 March 2006)

Semilocal density functional approximations (DFAs) for the exchange-correlation energy suffer from self-interaction error, which is believed to be the cause of many of the failures of common DFAs, such as poor description of charge transfer and transition states of chemical reactions. The standard self-interaction correction (SIC) of Perdew and Zunger mends some of these failures but spoils such essential properties as thermochemistry and equilibrium bond lengths. The Perdew-Zunger SIC seems to overcorrect many-electron systems. In this paper, we propose a modified SIC, which is scaled down in many-electron regions. The new SIC has an improved performance for many molecular properties, including total energies, atomization energies, barrier heights of chemical reactions, ionization potentials, electron affinities, and bond lengths. The local spin-density approximation (LSDA) benefits from SIC more than higher-level functionals do. The scaled-down SIC has only one adjustable parameter. Rationalization of the optimal value of this parameter enables us to construct an almost-nonempirical version of the scaled-down SIC-LSDA, which is significantly better than uncorrected LSDA and even better than the uncorrected generalized gradient approximation. We present an analysis of the formal properties of the scaled-down SIC and define possible directions for further improvements. In particular, we find that exactness for all one-electron densities does not guarantee correct asymptotics for the exchange-correlation potential of a many-electron system.

© 2006 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. METHODOLOGY
  3. COMPUTATIONAL DETAILS
  4. RESULTS
    1. Magnitudes of the correction
    2. Total energies of atoms
    3. Atomization energies
    4. Barrier heights of chemical reactions
    5. Ionization potentials and electron affinities
    6. Bond lengths
  5. DISCUSSION
    1. Effect of orbital densities on the functional dependence of the SIC results
    2. Formal properties and exact constraints on the parameter k
  6. CONCLUSIONS

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KEYWORDS and PACS

Keywords

density functional theory, dissociation energies, ionisation potential, electron affinity, bond lengths

PACS

  • 31.15.E-

    Density-functional theory

  • 33.15.Fm

    Bond strengths, dissociation energies

  • 33.15.Ry

    Ionization potentials, electron affinities, molecular core binding energy

  • 33.15.Dj

    Interatomic distances and angles

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.2176608

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

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