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Title: Benchmarking the GW Approximation and Bethe–Salpeter Equation for Groups IB and IIB Atoms and Monoxides

Abstract

Energies from the GW approximation and the Bethe–Salpeter equation (BSE) are benchmarked against the excitation energies of transition-metal (Cu, Zn, Ag, and Cd) single atoms and monoxide anions. We demonstrate that best estimates of GW quasiparticle energies at the complete basis set limit should be obtained via extrapolation or closure relations, while numerically converged GW-BSE eigenvalues can be obtained on a finite basis set. Calculations using real-space wave functions and pseudopotentials are shown to give best-estimate GW energies that agree (up to the extrapolation error) with calculations using all-electron Gaussian basis sets. We benchmark the effects of a vertex approximation (ΓLDA) and the mean-field starting point in GW and the BSE, performing computations using a real-space, transition-space basis and scalar-relativistic pseudopotentials. Here, while no variant of GW improves on perturbative G0W0 at predicting ionization energies, G0W0ΓLDA-BSE computations give excellent agreement with experimental absorption spectra as long as off-diagonal self-energy terms are included. We also present G0W0 quasiparticle energies for the CuO–, ZnO–, AgO–, and CdO– anions, in comparison to available anion photoelectron spectra.

Authors:
ORCiD logo; ; ;
Publication Date:
Research Org.:
Univ. of Illinois at Chicago, Chicago, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1351303
Grant/Contract Number:  
SC0001853
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 13; Journal Issue: 5; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 97 MATHEMATICS AND COMPUTING

Citation Formats

Hung, Linda, Bruneval, Fabien, Baishya, Kopinjol, and Öğüt, Serdar. Benchmarking the GW Approximation and Bethe–Salpeter Equation for Groups IB and IIB Atoms and Monoxides. United States: N. p., 2017. Web. doi:10.1021/acs.jctc.7b00123.
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Hung, Linda, Bruneval, Fabien, Baishya, Kopinjol, & Öğüt, Serdar. Benchmarking the GW Approximation and Bethe–Salpeter Equation for Groups IB and IIB Atoms and Monoxides. United States. https://doi.org/10.1021/acs.jctc.7b00123
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Hung, Linda, Bruneval, Fabien, Baishya, Kopinjol, and Öğüt, Serdar. Fri . "Benchmarking the GW Approximation and Bethe–Salpeter Equation for Groups IB and IIB Atoms and Monoxides". United States. https://doi.org/10.1021/acs.jctc.7b00123. https://www.osti.gov/servlets/purl/1351303.
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@article{osti_1351303,
title = {Benchmarking the GW Approximation and Bethe–Salpeter Equation for Groups IB and IIB Atoms and Monoxides},
author = {Hung, Linda and Bruneval, Fabien and Baishya, Kopinjol and Öğüt, Serdar},
abstractNote = {Energies from the GW approximation and the Bethe–Salpeter equation (BSE) are benchmarked against the excitation energies of transition-metal (Cu, Zn, Ag, and Cd) single atoms and monoxide anions. We demonstrate that best estimates of GW quasiparticle energies at the complete basis set limit should be obtained via extrapolation or closure relations, while numerically converged GW-BSE eigenvalues can be obtained on a finite basis set. Calculations using real-space wave functions and pseudopotentials are shown to give best-estimate GW energies that agree (up to the extrapolation error) with calculations using all-electron Gaussian basis sets. We benchmark the effects of a vertex approximation (ΓLDA) and the mean-field starting point in GW and the BSE, performing computations using a real-space, transition-space basis and scalar-relativistic pseudopotentials. Here, while no variant of GW improves on perturbative G0W0 at predicting ionization energies, G0W0ΓLDA-BSE computations give excellent agreement with experimental absorption spectra as long as off-diagonal self-energy terms are included. We also present G0W0 quasiparticle energies for the CuO–, ZnO–, AgO–, and CdO– anions, in comparison to available anion photoelectron spectra.},
doi = {10.1021/acs.jctc.7b00123},
journal = {Journal of Chemical Theory and Computation},
number = 5,
volume = 13,
place = {United States},
year = {Fri Apr 07 00:00:00 EDT 2017},
month = {Fri Apr 07 00:00:00 EDT 2017}
}
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https://doi.org/10.1021/acs.jctc.7b00123
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    Works referencing / citing this record:

    Practical GW scheme for electronic structure of 3 d -transition-metal monoxide anions: ScO−, TiO−, CuO−, and ZnO−
    journal, October 2019

    • Byun, Young-Moo; Öğüt, Serdar
    • The Journal of Chemical Physics, Vol. 151, Issue 13
    • DOI: 10.1063/1.5118671

    Modeling Excited States of Confined Systems
    book, January 2018

    Assessment of Ab Initio and Density Functional Theory Methods for the Excitations of Donor-Acceptor Complexes: The Case of the Benzene-Tetracyanoethylene Model
    journal, April 2018

    • Xu, Peng; Zhang, Cai-Rong; Wang, Wei
    • International Journal of Molecular Sciences, Vol. 19, Issue 4
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    Modeling Excited States of Confined Systems
    book, January 2020

    Density-Based Basis-Set Incompleteness Correction for GW Methods
    journal, December 2019

    • Loos, Pierre-François; Pradines, Barthélémy; Scemama, Anthony
    • Journal of Chemical Theory and Computation, Vol. 16, Issue 2
    • DOI: 10.1021/acs.jctc.9b01067
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