Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Practical GW scheme for electronic structure of 3d-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 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.

Authors:
ORCiD logo [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Illinois, Chicago, IL (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (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.
Copy to clipboard
Byun, Young-Moo, & Öğüt, Serdar. Practical GW scheme for electronic structure of 3d-transition-metal monoxide anions: ScO-, TiO-, CuO-, and ZnO-. United States. https://doi.org/10.1063/1.5118671
Copy to clipboard
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. https://doi.org/10.1063/1.5118671. https://www.osti.gov/servlets/purl/1577786.
Copy to clipboard
@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}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1063/1.5118671
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Optical excitations in organic molecules, clusters, and defects studied by first-principles Green’s function methods
journal, May 2006

Analyses of the ScO− and ScO2− photoelectron spectra
journal, July 2000

  • Gonzales, Jason M.; King, Rollin A.; Schaefer, Henry F.
  • The Journal of Chemical Physics, Vol. 113, Issue 2
  • DOI: 10.1063/1.481832

Quasiparticle GW calculations for solids, molecules, and two-dimensional materials
journal, June 2013

Evaluating the GW Approximation with CCSD(T) for Charged Excitations Across the Oligoacenes
journal, May 2016

  • Rangel, Tonatiuh; Hamed, Samia M.; Bruneval, Fabien
  • Journal of Chemical Theory and Computation, Vol. 12, Issue 6
  • DOI: 10.1021/acs.jctc.6b00163

Electronic Structure and Bonding of the Early 3d-Transition Metal Diatomic Oxides and Their Ions: ScO 0,± , TiO 0,± , CrO 0,± , and MnO 0,± †
journal, August 2010

  • Miliordos, Evangelos; Mavridis, Aristides
  • The Journal of Physical Chemistry A, Vol. 114, Issue 33
  • DOI: 10.1021/jp910218u

The GW -Method for Quantum Chemistry Applications: Theory and Implementation
journal, December 2012

  • van Setten, M. J.; Weigend, F.; Evers, F.
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 1
  • DOI: 10.1021/ct300648t

Unphysical Discontinuities in GW Methods
journal, August 2018

  • Véril, Mickaël; Romaniello, Pina; Berger, J. A.
  • Journal of Chemical Theory and Computation, Vol. 14, Issue 10
  • DOI: 10.1021/acs.jctc.8b00745

Fully self-consistent G W and quasiparticle self-consistent G W for molecules
journal, April 2014

Periodic trends in the diatomic monoxides and monosulfides of the 3d transition metals
journal, January 2000

  • Bridgeman, Adam J.; Rothery, Joanne
  • Journal of the Chemical Society, Dalton Transactions, Issue 2
  • DOI: 10.1039/a906523g

Self-consistent G W calculations for semiconductors and insulators
journal, June 2007

Benchmark Many-Body GW and Bethe–Salpeter Calculations for Small Transition Metal Molecules
journal, August 2014

  • Körbel, Sabine; Boulanger, Paul; Duchemin, Ivan
  • Journal of Chemical Theory and Computation, Vol. 10, Issue 9
  • DOI: 10.1021/ct5003658

The GW approximation: content, successes and limitations: The GW approximation
journal, December 2017

  • Reining, Lucia
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 8, Issue 3
  • DOI: 10.1002/wcms.1344

molgw 1: Many-body perturbation theory software for atoms, molecules, and clusters
journal, November 2016

  • Bruneval, Fabien; Rangel, Tonatiuh; Hamed, Samia M.
  • Computer Physics Communications, Vol. 208
  • DOI: 10.1016/j.cpc.2016.06.019

Electronic Structure of the 3d Metal Monoxide Anions
journal, June 2000

  • Gutsev, Gennady L.; Rao, B. K.; Jena, P.
  • The Journal of Physical Chemistry A, Vol. 104, Issue 22
  • DOI: 10.1021/jp000384f

Testing variations of the GW approximation on strongly correlated transition metal oxides: hematite (α-Fe2O3) as a benchmark
journal, January 2011

  • Liao, Peilin; Carter, Emily A.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 33
  • DOI: 10.1039/c1cp20829b

Explicitly Correlated Electrons in Molecules
journal, December 2011

  • Hättig, Christof; Klopper, Wim; Köhn, Andreas
  • Chemical Reviews, Vol. 112, Issue 1
  • DOI: 10.1021/cr200168z

Correction to Benchmarking the GW Approximation and Bethe–Salpeter Equation for Groups IB and IIB Monoxides
journal, October 2017

  • Hung, Linda; Bruneval, Fabien; Baishya, Kopinjol
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 11
  • DOI: 10.1021/acs.jctc.7b01054

Fully self-consistent GW calculations for molecules
journal, February 2010

Generalized Kohn-Sham schemes and the band-gap problem
journal, February 1996

Benchmark of G W methods for azabenzenes
journal, December 2012

Evaluation of ⟨Ŝ2⟩ in density functional theory
journal, June 2007

  • Cohen, Aron J.; Tozer, David J.; Handy, Nicholas C.
  • The Journal of Chemical Physics, Vol. 126, Issue 21
  • DOI: 10.1063/1.2737773

Quasiparticle band structure based on a generalized Kohn-Sham scheme
journal, September 2007

Relativity and the periodic system of elements
journal, August 1979

  • Pyykko, Pekka; Desclaux, Jean Paul
  • Accounts of Chemical Research, Vol. 12, Issue 8
  • DOI: 10.1021/ar50140a002

Chemical Bonding between Cu and OxygenCopper Oxides vs O 2 Complexes:  A Study of CuO x ( x = 0−6) Species by Anion Photoelectron Spectroscopy
journal, March 1997

  • Wu, Hongbin; Desai, Sunil R.; Wang, Lai-Sheng
  • The Journal of Physical Chemistry A, Vol. 101, Issue 11
  • DOI: 10.1021/jp9631442

Beyond the Tamm-Dancoff approximation for extended systems using exact diagonalization
journal, July 2015

Self-consistent GW calculations of electronic transport in thiol- and amine-linked molecular junctions
journal, March 2011

Excited states of the 3 d transition metal monoxides
journal, June 2003

  • Dai, Bing; Deng, Kaiming; Yang, Jinlong
  • The Journal of Chemical Physics, Vol. 118, Issue 21
  • DOI: 10.1063/1.1570811

Benchmark of GW Approaches for the GW 100 Test Set
journal, September 2016

  • Caruso, Fabio; Dauth, Matthias; van Setten, Michiel J.
  • Journal of Chemical Theory and Computation, Vol. 12, Issue 10
  • DOI: 10.1021/acs.jctc.6b00774

GW and Bethe-Salpeter study of small water clusters
journal, January 2016

  • Blase, Xavier; Boulanger, Paul; Bruneval, Fabien
  • The Journal of Chemical Physics, Vol. 144, Issue 3
  • DOI: 10.1063/1.4940139

Quasi-Particle Self-Consistent GW for Molecules
journal, May 2016

  • Kaplan, F.; Harding, M. E.; Seiler, C.
  • Journal of Chemical Theory and Computation, Vol. 12, Issue 6
  • DOI: 10.1021/acs.jctc.5b01238

The structures, electron affinities, and energetic stabilities of TiOn and TiOn− (n=1–3)
journal, March 1999

  • Walsh, Mary B.; King, Rollin A.; Schaefer, Henry F.
  • The Journal of Chemical Physics, Vol. 110, Issue 11
  • DOI: 10.1063/1.478418

Excitons in Solids from Time-Dependent Density-Functional Theory: Assessing the Tamm-Dancoff Approximation
journal, January 2017

On the low‐lying states of CuO
journal, September 1983

  • Bagus, Paul S.; Nelin, Constance J.; Bauschlicher, Charles W.
  • The Journal of Chemical Physics, Vol. 79, Issue 6
  • DOI: 10.1063/1.446126

Electronic structure of titanium oxide clusters: TiOy (y = 1−3) and (TiO2)n (n = 1−4)
journal, November 1997

  • Wu, Hongbin; Wang, Lai‐Sheng
  • The Journal of Chemical Physics, Vol. 107, Issue 20
  • DOI: 10.1063/1.475026

Relativistic Effects in Chemistry: More Common Than You Thought
journal, May 2012

Electron correlation in semiconductors and insulators: Band gaps and quasiparticle energies
journal, October 1986

Benchmarking the GW Approximation and Bethe–Salpeter Equation for Groups IB and IIB Atoms and Monoxides
journal, April 2017

  • Hung, Linda; Bruneval, Fabien; Baishya, Kopinjol
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 5
  • DOI: 10.1021/acs.jctc.7b00123

On correlation effects in electron spectroscopies and the GW approximation
journal, October 1999

Converging self-consistent field equations in quantum chemistry – recent achievements and remaining challenges
journal, March 2007

  • Kudin, Konstantin N.; Scuseria, Gustavo E.
  • ESAIM: Mathematical Modelling and Numerical Analysis, Vol. 41, Issue 2
  • DOI: 10.1051/m2an:2007022

Ionization energy of atoms obtained from GW self-energy or from random phase approximation total energies
journal, May 2012

  • Bruneval, Fabien
  • The Journal of Chemical Physics, Vol. 136, Issue 19
  • DOI: 10.1063/1.4718428

Dynamical effects in electron spectroscopy
journal, November 2015

  • Zhou, Jianqiang Sky; Kas, J. J.; Sponza, Lorenzo
  • The Journal of Chemical Physics, Vol. 143, Issue 18
  • DOI: 10.1063/1.4934965

GW 100: A Plane Wave Perspective for Small Molecules
journal, January 2017

  • Maggio, Emanuele; Liu, Peitao; van Setten, Michiel J.
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 2
  • DOI: 10.1021/acs.jctc.6b01150

VESTA : a three-dimensional visualization system for electronic and structural analysis
journal, May 2008

GW in the Gaussian and Plane Waves Scheme with Application to Linear Acenes
journal, July 2016

  • Wilhelm, Jan; Del Ben, Mauro; Hutter, Jürg
  • Journal of Chemical Theory and Computation, Vol. 12, Issue 8
  • DOI: 10.1021/acs.jctc.6b00380

GW 100: Benchmarking G 0 W 0 for Molecular Systems
journal, November 2015

  • van Setten, Michiel J.; Caruso, Fabio; Sharifzadeh, Sahar
  • Journal of Chemical Theory and Computation, Vol. 11, Issue 12
  • DOI: 10.1021/acs.jctc.5b00453

Relativistic effects in structural chemistry
journal, May 1988

Relativistic and correlation effects in CuH, AgH, and AuH: Comparison of various relativistic methods
journal, February 1995

  • Collins, Charlene L.; Dyall, Kenneth G.; Schaefer, Henry F.
  • The Journal of Chemical Physics, Vol. 102, Issue 5
  • DOI: 10.1063/1.468724

Potential Energy Curves and Electronic Structure of Copper Nitrides CuN and CuN+Versus CuO and CuO+
journal, March 1999

  • Daoudi, A.; Touimi Benjelloun, A.; Flament, J. P.
  • Journal of Molecular Spectroscopy, Vol. 194, Issue 1
  • DOI: 10.1006/jmsp.1998.7596

Similarities and differences in the structure of 3 d -metal monocarbides and monoxides
journal, July 2003

  • Gutsev, Gennady L.; Andrews, Lester; Bauschlicher, Jr., Charles W.
  • Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 109, Issue 6
  • DOI: 10.1007/s00214-003-0428-4

Theoretical study of low-lying electronic states of CuO and CuO−
journal, August 2000

GW100: Comparison of Methods and Accuracy of Results Obtained with the WEST Code
journal, February 2018

  • Govoni, Marco; Galli, Giulia
  • Journal of Chemical Theory and Computation, Vol. 14, Issue 4
  • DOI: 10.1021/acs.jctc.7b00952

Effects of relativity and of the lanthanide contraction on the atoms from hafnium to bismuth
journal, June 1975

Beyond the quasiparticle approximation: Fully self-consistent G W calculations
journal, October 2018

The electronic structure of ZnO and ZnF determined by anion photoelectron spectroscopy
journal, June 2001

  • Moravec, Vicki D.; Klopcic, Stephen A.; Chatterjee, Bappaditya
  • Chemical Physics Letters, Vol. 341, Issue 3-4
  • DOI: 10.1016/s0009-2614(01)00465-1

Benchmarking the Starting Points of the GW Approximation for Molecules
journal, December 2012

  • Bruneval, Fabien; Marques, Miguel A. L.
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 1
  • DOI: 10.1021/ct300835h

Predictive G W calculations using plane waves and pseudopotentials
journal, August 2014

Exchange and Correlation Effects in Electronic Excitations of Cu 2 O
journal, December 2006

Core-Level Binding Energies from GW : An Efficient Full-Frequency Approach within a Localized Basis
journal, August 2018

  • Golze, Dorothea; Wilhelm, Jan; van Setten, Michiel J.
  • Journal of Chemical Theory and Computation, Vol. 14, Issue 9
  • DOI: 10.1021/acs.jctc.8b00458

Relativistic Effects in the Electronic Structure of Atoms
journal, September 2017

Importance of reference Hamiltonians containing exact exchange for accurate one-shot G W calculations of Cu 2 O
journal, June 2012

A comparison of ZnO and ZnO−
journal, November 1998

  • Bauschlicher, Charles W.; Partridge, Harry
  • The Journal of Chemical Physics, Vol. 109, Issue 19
  • DOI: 10.1063/1.477506

Photoelectron spectra of copper oxide cluster anions from first principles methods
journal, August 2018

  • Shi, Bin; Weissman, Shira; Bruneval, Fabien
  • The Journal of Chemical Physics, Vol. 149, Issue 6
  • DOI: 10.1063/1.5038744

Zinc oxide and its anion: A negative ion photoelectron spectroscopic study
journal, November 1998

  • Fancher, C. A.; de Clercq, H. L.; Thomas, O. C.
  • The Journal of Chemical Physics, Vol. 109, Issue 19
  • DOI: 10.1063/1.477505

Photoelectron Spectroscopy and Electronic Structure of ScO n - ( n = 1−4) and YO n - ( n = 1−5):  Strong Electron Correlation Effects in ScO - and YO -
journal, November 1998

  • Wu, Hongbin; Wang, Lai-Sheng
  • The Journal of Physical Chemistry A, Vol. 102, Issue 46
  • DOI: 10.1021/jp982588q

GW in the Gaussian and plane waves scheme with application to linear acenes
text, January 2016

  • Wilhelm, Jan; Del Ben, Mauro; Hutter, Jürg
  • American Chemical Society (ACS)
  • DOI: 10.5167/uzh-128624

GW 100: Benchmarking G0W0 for molecular systems
text, January 2015

  • van Setten, M. J.; Caruso, F.; Sharifzadeh, S.
  • Universität Regensburg
  • DOI: 10.5283/epub.33561

Fully selfconsistent GW calculations for molecules
text, January 2010

Predictive GW calculations using plane waves and pseudopotentials
text, January 2014

Evaluating the GW Approximation with CCSD(T) for Charged Excitations Across the Oligoacenes
text, January 2016

Quasiparticle band structure based on a generalized Kohn-Sham scheme
text, January 2006

    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: