Exchangecorrelation energies of atoms from efficient density functionals: influence of the electron density
Abstract
The primary goal of Kohn–Sham density functional theory is to evaluate the exchangecorrelation 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 spindensity approximation (LSDA), Perdew–Burke–Ernzerhof (PBE), Tao–Perdew–Staroverov–Scuseria (TPSS), and hybrid functional PBE0. We find that the spinrestricted 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 selfconsistent densities. We further find that the quality of the electron density have greater effect on the exchangecorrelation energies of kinetic energy densitydependent metaGGA functionals TPSS and TM than on those of the LSDA and GGA, and therefore, should have greater influence on the performance of metaGGA 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.
 Authors:

 Temple Univ., Philadelphia, PA (United States)
 Peking Univ., Beijing (People's Republic of China)
 National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)
 Publication Date:
 Research Org.:
 National Energy Technology Lab. (NETL), Pittsburgh, PA, and Morgantown, WV (United States). Inhouse Research
 Sponsoring Org.:
 USDOE
 OSTI Identifier:
 1413214
 Report Number(s):
 NETLPUB21537
Journal ID: ISSN 09534075
 Grant/Contract Number:
 CHE 1640584
 Resource Type:
 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 09534075
 Publisher:
 IOP Publishing
 Country of Publication:
 United States
 Language:
 English
 Subject:
 74 ATOMIC AND MOLECULAR PHYSICS; exchangecorrelation energies; density functional theory; TaoMo semilocal functional
Citation Formats
Tao, Jianmin, Ye, Lin Hui, and Duan, Yuhua. Exchangecorrelation energies of atoms from efficient density functionals: influence of the electron density. United States: N. p., 2017.
Web. doi:10.1088/13616455/aa95b1.
Tao, Jianmin, Ye, Lin Hui, & Duan, Yuhua. Exchangecorrelation energies of atoms from efficient density functionals: influence of the electron density. United States. doi:10.1088/13616455/aa95b1.
Tao, Jianmin, Ye, Lin Hui, and Duan, Yuhua. Mon .
"Exchangecorrelation energies of atoms from efficient density functionals: influence of the electron density". United States. doi:10.1088/13616455/aa95b1. https://www.osti.gov/servlets/purl/1413214.
@article{osti_1413214,
title = {Exchangecorrelation energies of atoms from efficient density functionals: influence of the electron density},
author = {Tao, Jianmin and Ye, Lin Hui and Duan, Yuhua},
abstractNote = {The primary goal of Kohn–Sham density functional theory is to evaluate the exchangecorrelation 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 spindensity approximation (LSDA), Perdew–Burke–Ernzerhof (PBE), Tao–Perdew–Staroverov–Scuseria (TPSS), and hybrid functional PBE0. We find that the spinrestricted 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 selfconsistent densities. We further find that the quality of the electron density have greater effect on the exchangecorrelation energies of kinetic energy densitydependent metaGGA functionals TPSS and TM than on those of the LSDA and GGA, and therefore, should have greater influence on the performance of metaGGA 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.},
doi = {10.1088/13616455/aa95b1},
journal = {Journal of Physics. B, Atomic, Molecular and Optical Physics},
number = 24,
volume = 50,
place = {United States},
year = {2017},
month = {11}
}