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Fermi-Löwdin-orbital self-interaction correction using the optimized-effective-potential method within the Krieger-Li-Iafrate approximation

Journal Article · · Physical Review A
 [1];  [2];  [2]
  1. Univ. of Texas at El Paso, TX (United States); Central Michigan University
  2. Univ. of Texas at El Paso, TX (United States)
+ Show Author Affiliations
Perdew-Zunger self-interaction correction (PZ-SIC) offers a route to remove self interaction errors on an orbital-by-orbital basis. A recent formulation of PZ-SIC by Pederson, Ruzsinszky and Perdew proposes restricting the unitary transformation to localized orbitals called Fermi-Löwdin orbitals. This formulation, called the FLOSIC method, simplifies PZ-SIC calculations and was implemented self-consistently using a Jacobi-like (FLOSIC-Jacobi) iteration scheme. In this work we implement the FLOSIC approach using the Krieger-Li-Iafrate (KLI) approximation to the optimized effective potential (OEP). We compare the results of present FLOSIC-KLI approach with FLOSIC-Jacobi scheme for atomic energies, atomization energies, ionization energies, barrier heights, polarizability of chains of hydrogen molecules etc. to validate the FLOSIC-KLI approach. The FLOSICKLI approach, which is within the realm of Kohn-Sham theory, predicts smaller energy gaps between frontier orbitals due to the lowering of eigenvalues of the lowest unoccupied orbitals. Results show that atomic energies, atomization energies, ionization energy as an absolute of highest occupied orbital eigenvalue, and polarizability of chains of hydrogen molecules between the two methods agree within 2%. Lastly the FLOSIC-KLI approach is used to determine the vertical ionization energies of water clusters.
Research Organization:
Central Michigan Univ., Mount Pleasant, MI (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
SC0018331
OSTI ID:
1781837
Journal Information:
Physical Review A, Journal Name: Physical Review A Journal Issue: 4 Vol. 103; ISSN 2469-9926
Publisher:
American Physical Society (APS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
Atomic & molecular structure
Density functional theory
Electronic structure
Electronic structure of atoms & molecules
First-principles calculations