Stretched or noded orbital densities and self-interaction correction in density functional theory

Shahi, Chandra; Bhattarai, Puskar; Wagle, Kamal; Santra, Biswajit; Schwalbe, Sebastian; Hahn, Torsten; Kortus, Jens; Jackson, Koblar A.; Peralta, Juan E.; Trepte, Kai; Lehtola, Susi; Nepal, Niraj K.; Myneni, Hemanadhan; Neupane, Bimal; Adhikari, Santosh; Ruzsinszky, Adrienn; Yamamoto, Yoh; Baruah, Tunna; Zope, Rajendra R.; Perdew, John P.

doi:10.1063/1.5087065

Title: Stretched or noded orbital densities and self-interaction correction in density functional theory

Journal Article · Wed May 01 00:00:00 EDT 2019 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5087065· OSTI ID:1566662

Shahi, Chandra ^[1];

^[1];

^[2];

^[3];

^[4];

^[1];

^[1]; Adhikari, Santosh ^[1]; Ruzsinszky, Adrienn ^[1]; Yamamoto, Yoh ^[5]; Baruah, Tunna ^[5]; Zope, Rajendra R. ^[5];

^[1]

Temple Univ., Philadelphia, PA (United States)
TU Bergakademie Freiberg (Germany)
Central Michigan Univ., Mount Pleasant, MI (United States)
Univ. of Helsinki (Finland)
Univ. of Texas, El Paso, TX (United States)

Semilocal approximations to the density functional for the exchange-correlation energy of a many-electron system necessarily fail for lobed one-electron densities, including not only the familiar stretched densities but also the less familiar but closely related noded ones. The Perdew-Zunger (PZ) self-interaction correction (SIC) to a semilocal approximation makes that approximation exact for all one-electron ground- or excited-state densities and accurate for stretched bonds. When the minimization of the PZ total energy is made over real localized orbitals, the orbital densities can be noded, leading to energy errors in many-electron systems. Minimization over complex localized orbitals yields nodeless orbital densities, which reduce but typically do not eliminate the SIC errors of atomization energies. Other errors of PZ SIC remain, attributable to the loss of the exact constraints and appropriate norms that the semilocal approximations satisfy, suggesting the need for a generalized SIC. These conclusions are supported by calculations for one-electron densities and for many-electron molecules. While PZ SIC raises and improves the energy barriers of standard generalized gradient approximations (GGAs) and meta-GGAs, it reduces and often worsens the atomization energies of molecules. Thus, PZ SIC raises the energy more as the nodality of the valence localized orbitals increases from atoms to molecules to transition states. PZ SIC is applied here, in particular, to the strongly constrained and appropriately normed (SCAN) meta-GGA, for which the correlation part is already self-interaction-free. This property makes SCAN a natural first candidate for a generalized SIC.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Complex Materials from First Principles (CCM); Temple Univ., Philadelphia, PA (United States); Central Michigan Univ., Mount Pleasant, MI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012575; SC0018331

OSTI ID:: 1566662

Alternate ID(s):: OSTI ID: 1510163

Journal Information:: Journal of Chemical Physics, Vol. 150, Issue 17; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 38 works

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Title: Stretched or noded orbital densities and self-interaction correction in density functional theory

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