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Title: Practical GW scheme for electronic structure of 3 d-transition-metal monoxide anions: ScO -, TiO -, CuO -, and ZnO -

Abstract

The GW approximation to many-body perturbation theory is a reliable tool for describing charged electronic excitations, and it has been successfully applied to a wide range of extended systems for several decades using a plane-wave basis. However, the GW approximation has been used to test limited spectral properties of a limited set of finite systems (e.g., frontier orbital energies of closed-shell sp molecules) only for about a decade using a local-orbital basis. Here, we calculate the quasiparticle spectra of closed- and open-shell molecular anions with partially and completely filled 3 d shells (shallow and deep 3 d states, respectively), ScO -, TiO -, CuO -, and ZnO -, using various levels of GW theory, and compare them to experiments to evaluate the performance of the GW approximation on the electronic structure of small molecules containing 3 d transition metals. We find that the G-only eigenvalue self-consistent GW scheme with W fixed to the PBE level ($$G_nW_0$$@PBE), which gives the best compromise between accuracy and efficiency for solids, also gives good results for both localized ( d) and delocalized ( sp) states of 3 d-transition-metal oxide molecules. The success of $$G_nW_0$$@PBE in predicting electronic excitations in these systems reasonably well is likely due to the fortuitous cancellation effect between the overscreening of the Coulomb interaction by PBE and the underscreening by the neglect of vertex corrections. Together with the absence of the self-consistent field convergence error (e.g., spin contamination in open-shell systems) and the GW multisolution issue, the $$G_nW_0$$@PBE scheme gives the possibility to predict the electronic structure of complex real systems (e.g., molecule-solid and sp-d hybrid systems) accurately and efficiently.

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Illinois, Chicago, IL (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States); Univ. of Illinois at Urbana-Champaign, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1577786
Alternate Identifier(s):
OSTI ID: 1568949
Grant/Contract Number:  
AC02-05CH11231; SC0017824
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 13; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Physics

Citation Formats

Byun, Young-Moo, and Öğüt, Serdar. Practical GW scheme for electronic structure of 3d-transition-metal monoxide anions: ScO-, TiO-, CuO-, and ZnO-. United States: N. p., 2019. Web. doi:10.1063/1.5118671.
Byun, Young-Moo, & Öğüt, Serdar. Practical GW scheme for electronic structure of 3d-transition-metal monoxide anions: ScO-, TiO-, CuO-, and ZnO-. United States. doi:10.1063/1.5118671.
Byun, Young-Moo, and Öğüt, Serdar. Mon . "Practical GW scheme for electronic structure of 3d-transition-metal monoxide anions: ScO-, TiO-, CuO-, and ZnO-". United States. doi:10.1063/1.5118671. https://www.osti.gov/servlets/purl/1577786.
@article{osti_1577786,
title = {Practical GW scheme for electronic structure of 3d-transition-metal monoxide anions: ScO-, TiO-, CuO-, and ZnO-},
author = {Byun, Young-Moo and Öğüt, Serdar},
abstractNote = {The GW approximation to many-body perturbation theory is a reliable tool for describing charged electronic excitations, and it has been successfully applied to a wide range of extended systems for several decades using a plane-wave basis. However, the GW approximation has been used to test limited spectral properties of a limited set of finite systems (e.g., frontier orbital energies of closed-shell sp molecules) only for about a decade using a local-orbital basis. Here, we calculate the quasiparticle spectra of closed- and open-shell molecular anions with partially and completely filled 3d shells (shallow and deep 3d states, respectively), ScO-, TiO-, CuO-, and ZnO-, using various levels of GW theory, and compare them to experiments to evaluate the performance of the GW approximation on the electronic structure of small molecules containing 3d transition metals. We find that the G-only eigenvalue self-consistent GW scheme with W fixed to the PBE level ($G_nW_0$@PBE), which gives the best compromise between accuracy and efficiency for solids, also gives good results for both localized (d) and delocalized (sp) states of 3d-transition-metal oxide molecules. The success of $G_nW_0$@PBE in predicting electronic excitations in these systems reasonably well is likely due to the fortuitous cancellation effect between the overscreening of the Coulomb interaction by PBE and the underscreening by the neglect of vertex corrections. Together with the absence of the self-consistent field convergence error (e.g., spin contamination in open-shell systems) and the GW multisolution issue, the $G_nW_0$@PBE scheme gives the possibility to predict the electronic structure of complex real systems (e.g., molecule-solid and sp-d hybrid systems) accurately and efficiently.},
doi = {10.1063/1.5118671},
journal = {Journal of Chemical Physics},
number = 13,
volume = 151,
place = {United States},
year = {2019},
month = {10}
}

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