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Title: Exchange-correlation energies of atoms from efficient density functionals: influence of the electron density

The primary goal of Kohn–Sham density functional theory is to evaluate the exchange-correlation contribution to electronic properties. However, the accuracy of a density functional can be affected by the electron density. Here we apply the nonempirical Tao–Mo (TM) semilocal functional to study the influence of the electron density on the exchange and correlation energies of atoms and ions, and compare the results with the commonly used nonempirical semilocal functionals local spin-density approximation (LSDA), Perdew–Burke–Ernzerhof (PBE), Tao–Perdew–Staroverov–Scuseria (TPSS), and hybrid functional PBE0. We find that the spin-restricted Hartree–Fock density yields the exchange and correlation energies in good agreement with the Optimized Effective Potential method, particularly for spherical atoms and ions. However, the errors of these semilocal and hybrid functionals become larger for self-consistent densities. We further find that the quality of the electron density have greater effect on the exchange-correlation energies of kinetic energy density-dependent meta-GGA functionals TPSS and TM than on those of the LSDA and GGA, and therefore, should have greater influence on the performance of meta-GGA functionals. Lastly, we show that the influence of the density quality on PBE0 is slightly reduced, compared to that of PBE, due to the exact mixing.
ORCiD logo [1] ;  [2] ;  [3]
  1. Temple Univ., Philadelphia, PA (United States)
  2. Peking Univ., Beijing (People's Republic of China)
  3. National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)
Publication Date:
Report Number(s):
Journal ID: ISSN 0953-4075
Grant/Contract Number:
CHE 1640584
Accepted Manuscript
Journal Name:
Journal of Physics. B, Atomic, Molecular and Optical Physics
Additional Journal Information:
Journal Volume: 50; Journal Issue: 24; Journal ID: ISSN 0953-4075
IOP Publishing
Research Org:
National Energy Technology Lab. (NETL), Pittsburgh, PA, and Morgantown, WV (United States). In-house Research
Sponsoring Org:
Country of Publication:
United States
74 ATOMIC AND MOLECULAR PHYSICS; exchange-correlation energies; density functional theory; Tao-Mo semilocal functional
OSTI Identifier: