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Self-interaction-corrected Kohn–Sham effective potentials using the density-consistent effective potential method

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/5.0056561· OSTI ID:1852600
 [1];  [2];  [3];  [2];  [3];  [2];  [2]
  1. Univ. of Texas at El Paso, TX (United States); Univ. of Texas at El Paso, TX (United States)
  2. Univ. of Texas at El Paso, TX (United States)
  3. Temple Univ., Philadelphia, PA (United States)
+ Show Author Affiliations
Density functional theory (DFT) and beyond-DFT methods are often used in combination with photoelectron spectroscopy to obtain physical insights into the electronic structure of molecules and solids. The Kohn–Sham eigenvalues are not electron removal energies except for the highest occupied orbital. The eigenvalues of the highest occupied molecular orbitals often underestimate the electron removal or ionization energies due to the self-interaction (SI) errors in approximate density functionals. Here, we adapt and implement the density-consistent effective potential method of Kohut, Ryabinkin, and Staroverov (2014) to obtain SI-corrected local effective potentials from the SI-corrected Fermi–Löwdin orbitals and density in the Fermi–Löwdin orbital self-interaction correction scheme. The implementation is used to obtain the density of states (photoelectron spectra) and HOMO–LUMO gaps for a set of molecules and polyacenes. Good agreement with experimental values is obtained compared to a range of SI uncorrected density functional approximations.
Research Organization:
Central Michigan Univ., Mount Pleasant, MI (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0018331
OSTI ID:
1852600
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 6 Vol. 155; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
HOMO and LUMO
atomic structure
average local ionization energy
density functional theory
electron density
electrostatics
ions and properties
operator theory
photoelectron spectroscopy
self consistent field methods