Fermi orbital derivatives in self-interaction corrected density functional theory: Applications to closed shell atoms

doi:10.1063/1.4907592

Title: Fermi orbital derivatives in self-interaction corrected density functional theory: Applications to closed shell atoms

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Abstract

A recent modification of the Perdew-Zunger self-interaction-correction to the density-functional formalism has provided a framework for explicitly restoring unitary invariance to the expression for the total energy. The formalism depends upon construction of Löwdin orthonormalized Fermi-orbitals which parametrically depend on variational quasi-classical electronic positions. Derivatives of these quasi-classical electronic positions, required for efficient minimization of the self-interaction corrected energy, are derived and tested, here, on atoms. Total energies and ionization energies in closed-shell singlet atoms, where correlation is less important, using the Perdew-Wang 1992 Local Density Approximation (PW92) functional, are in good agreement with experiment and non-relativistic quantum-Monte-Carlo results albeit slightly too low.

Authors:

Pederson, Mark R., E-mail: mark.pederson@science.doe.gov ^[1]

Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218 (United States)

Publication Date:: Sat Feb 14 00:00:00 EST 2015

OSTI Identifier:: 22416098

Resource Type:: Journal Article

Journal Name:: Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 142; Journal Issue: 6; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606

Country of Publication:: United States

Language:: English

Subject:: 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; APPROXIMATIONS; ATOMS; CORRECTIONS; CORRELATIONS; DENSITY; DENSITY FUNCTIONAL METHOD; ELECTRONIC STRUCTURE; MINIMIZATION; MODIFICATIONS; MONTE CARLO METHOD; RELATIVISTIC RANGE

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                    Pederson, Mark R., E-mail: mark.pederson@science.doe.gov. Fermi orbital derivatives in self-interaction corrected density functional theory: Applications to closed shell atoms.  United States: N. p., 2015. 
        Web.  doi:10.1063/1.4907592.

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                    Pederson, Mark R., E-mail: mark.pederson@science.doe.gov. Fermi orbital derivatives in self-interaction corrected density functional theory: Applications to closed shell atoms.  United States.  https://doi.org/10.1063/1.4907592

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                    Pederson, Mark R., E-mail: mark.pederson@science.doe.gov. 2015.  
        "Fermi orbital derivatives in self-interaction corrected density functional theory: Applications to closed shell atoms".  United States.  https://doi.org/10.1063/1.4907592.

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@article{osti_22416098,

  title        = {Fermi orbital derivatives in self-interaction corrected density functional theory: Applications to closed shell atoms},

  author       = {Pederson, Mark R., E-mail: mark.pederson@science.doe.gov},

  abstractNote = {A recent modification of the Perdew-Zunger self-interaction-correction to the density-functional formalism has provided a framework for explicitly restoring unitary invariance to the expression for the total energy. The formalism depends upon construction of Löwdin orthonormalized Fermi-orbitals which parametrically depend on variational quasi-classical electronic positions. Derivatives of these quasi-classical electronic positions, required for efficient minimization of the self-interaction corrected energy, are derived and tested, here, on atoms. Total energies and ionization energies in closed-shell singlet atoms, where correlation is less important, using the Perdew-Wang 1992 Local Density Approximation (PW92) functional, are in good agreement with experiment and non-relativistic quantum-Monte-Carlo results albeit slightly too low.},

  doi          = {10.1063/1.4907592},

  url          = {https://www.osti.gov/biblio/22416098},
  journal      = {Journal of Chemical Physics},

  issn         = {0021-9606},

  number       = 6,

  volume       = 142,

  place        = {United States},

  year         = {Sat Feb 14 00:00:00 EST 2015},

  month        = {Sat Feb 14 00:00:00 EST 2015}

}

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