skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Photoelectron spectra of copper oxide cluster anions from first principles methods

Abstract

We present results and analyses for the photoelectron spectra of small copper oxide cluster anions (CuO, CuO2, CuO3, and Cu2O). The spectra are computed using various techniques, including density functional theory (DFT) with semi-local, global hybrid, and optimally tuned range-separated hybrid functionals, as well as many-body perturbation theory within the GW approximation based on various DFT starting points. The results are compared with each other and with the available experimental data. We conclude that as in many metal-organic systems, self-interaction errors are a major issue that is mitigated by hybrid functionals. However, these need to be balanced against a strong role of non-dynamical correlation—especially in smaller, more symmetric systems—where errors are alleviated by semi-local functionals. In conclusion, the relative importance of the two phenomena, including practical ways of balancing the two constraints, is discussed in detail.

Authors:
 [1];  [2];  [3];  [2];  [1]
  1. Univ. of Illinois, Chicago, IL (United States)
  2. Weizmann Institute of Science, Rehovoth (Israel)
  3. Univ. Paris-Saclay, Gif-sur-Yvette (France)
Publication Date:
Research Org.:
Univ. of Illinois, Chicago, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1511172
Alternate Identifier(s):
OSTI ID: 1464319
Grant/Contract Number:  
SC0017824; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 149; Journal Issue: 6; 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

Citation Formats

Shi, Bin, Weissman, Shira, Bruneval, Fabien, Kronik, Leeor, and Öğüt, Serdar. Photoelectron spectra of copper oxide cluster anions from first principles methods. United States: N. p., 2018. Web. doi:10.1063/1.5038744.
Shi, Bin, Weissman, Shira, Bruneval, Fabien, Kronik, Leeor, & Öğüt, Serdar. Photoelectron spectra of copper oxide cluster anions from first principles methods. United States. doi:https://doi.org/10.1063/1.5038744
Shi, Bin, Weissman, Shira, Bruneval, Fabien, Kronik, Leeor, and Öğüt, Serdar. Mon . "Photoelectron spectra of copper oxide cluster anions from first principles methods". United States. doi:https://doi.org/10.1063/1.5038744. https://www.osti.gov/servlets/purl/1511172.
@article{osti_1511172,
title = {Photoelectron spectra of copper oxide cluster anions from first principles methods},
author = {Shi, Bin and Weissman, Shira and Bruneval, Fabien and Kronik, Leeor and Öğüt, Serdar},
abstractNote = {We present results and analyses for the photoelectron spectra of small copper oxide cluster anions (CuO–, CuO–2, CuO–3, and Cu2O–). The spectra are computed using various techniques, including density functional theory (DFT) with semi-local, global hybrid, and optimally tuned range-separated hybrid functionals, as well as many-body perturbation theory within the GW approximation based on various DFT starting points. The results are compared with each other and with the available experimental data. We conclude that as in many metal-organic systems, self-interaction errors are a major issue that is mitigated by hybrid functionals. However, these need to be balanced against a strong role of non-dynamical correlation—especially in smaller, more symmetric systems—where errors are alleviated by semi-local functionals. In conclusion, the relative importance of the two phenomena, including practical ways of balancing the two constraints, is discussed in detail.},
doi = {10.1063/1.5038744},
journal = {Journal of Chemical Physics},
number = 6,
volume = 149,
place = {United States},
year = {2018},
month = {8}
}

Works referenced in this record:

Structural and electronic properties of small CuOm clusters
journal, March 2004


Assessment of a long-range corrected hybrid functional
journal, December 2006

  • Vydrov, Oleg A.; Scuseria, Gustavo E.
  • The Journal of Chemical Physics, Vol. 125, Issue 23
  • DOI: 10.1063/1.2409292

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


Thermal effects in the photoelectron spectra of Na N clusters ( N = 4 1 9 )
journal, October 2003


Optical spectra of CuO2 and matrix effect upon its structure
journal, September 2000

  • Caspary, N.; Savchenko, E. V.; Thoma, A.
  • Low Temperature Physics, Vol. 26, Issue 9
  • DOI: 10.1063/1.1312402

Molecular structures and vibrations of neutral and anionic CuO x ( x = 1 3 , 6 ) clusters
journal, February 2004


Outer-valence Electron Spectra of Prototypical Aromatic Heterocycles from an Optimally Tuned Range-Separated Hybrid Functional
journal, April 2014

  • Egger, David A.; Weissman, Shira; Refaely-Abramson, Sivan
  • Journal of Chemical Theory and Computation, Vol. 10, Issue 5
  • DOI: 10.1021/ct400956h

Reparameterization of hybrid functionals based on energy differences of states of different multiplicity
journal, December 2001

  • Reiher, Markus; Salomon, Oliver; Artur Hess, Bernd
  • Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 107, Issue 1
  • DOI: 10.1007/s00214-001-0300-3

Accurate Ionization Potentials and Electron Affinities of Acceptor Molecules III: A Benchmark of GW Methods
journal, January 2016

  • Knight, Joseph W.; Wang, Xiaopeng; Gallandi, Lukas
  • Journal of Chemical Theory and Computation, Vol. 12, Issue 2
  • DOI: 10.1021/acs.jctc.5b00871

Photoemission Spectra and Structures of Si Clusters at Finite Temperature
journal, July 1995


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

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

Ab initio and density functional study of spectroscopic properties of CuO and CuS
journal, March 2006


Electronic structure of copper phthalocyanine from G 0 W 0 calculations
journal, November 2011


An ab initio calculation of the electronic structure of copper dioxide
journal, December 1985


Strategy for finding a reliable starting point for G 0 W 0 demonstrated for molecules
journal, July 2012


Dynamical and Nondynamical Correlation
journal, January 1996

  • Mok, Daniel K. W.; Neumann, Ralf; Handy, Nicholas C.
  • The Journal of Physical Chemistry, Vol. 100, Issue 15
  • DOI: 10.1021/jp9528020

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

Electronic structure of the linear form of OCuO
journal, March 1991


B3LYP density functional study on spectroscopic properties of CuO− and CuS−
journal, January 2005

  • Midda, S.; Bera, N. C.; Das, A. K.
  • International Journal of Quantum Chemistry, Vol. 105, Issue 1
  • DOI: 10.1002/qua.20673

Benchmark of G W methods for azabenzenes
journal, December 2012


Excited states properties of organic molecules: from density functional theory to the GW and Bethe–Salpeter Green's function formalisms
journal, March 2014

  • Faber, C.; Boulanger, P.; Attaccalite, C.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 372, Issue 2011
  • DOI: 10.1098/rsta.2013.0271

A new mixing of Hartree–Fock and local density‐functional theories
journal, January 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 2
  • DOI: 10.1063/1.464304

Density functional theory study of the structures and stabilities of CuO and CuO3
journal, January 2000


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

DFT calculations of <mml:math altimg="si16.gif" display="inline" overflow="scroll" xmlns:xocs="http://www.elsevier.com/xml/xocs/dtd" xmlns:xs="http://www.w3.org/2001/XMLSchema" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xmlns="http://www.elsevier.com/xml/ja/dtd" xmlns:ja="http://www.elsevier.com/xml/ja/dtd" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:tb="http://www.elsevier.com/xml/common/table/dtd" xmlns:sb="http://www.elsevier.com/xml/common/struct-bib/dtd" xmlns:ce="http://www.elsevier.com/xml/common/dtd" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:cals="http://www.elsevier.com/xml/common/cals/dtd"><mml:mrow><mml:msub><mml:mrow><mml:mtext>Cu</mml:mtext></mml:mrow><mml:mrow><mml:mi>n</mml:mi></mml:mrow></mml:msub><mml:msubsup><mml:mrow><mml:mtext>O</mml:mtext></mml:mrow><mml:mrow><mml:mi>m</mml:mi></mml:mrow><mml:mrow><mml:mn>0</mml:mn><mml:mo>/</mml:mo><mml:mo>+</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math> clusters: Evidence for Cu2O building blocks
journal, April 2008


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

Structure, Bonding, and Relative Stability of the Ground and Low-Lying Electronic States of CuO 2 . The Role of Exact Exchange
journal, February 2009

  • Güell, Mireia; Luis, Josep M.; Rodríguez-Santiago, Luís
  • The Journal of Physical Chemistry A, Vol. 113, Issue 7
  • DOI: 10.1021/jp8031379

NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010

  • Valiev, M.; Bylaska, E. J.; Govind, N.
  • Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489
  • DOI: 10.1016/j.cpc.2010.04.018

The adiabatic connection method: a non-empirical hybrid
journal, January 1997


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

First-principles modeling of localized d states with the G W @ LDA + U approach
journal, July 2010


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

A theoretical study of the CuO3 species
journal, November 2000

  • Deng, Ke; Yang, Jinlong; Zhu, Qingshi
  • The Journal of Chemical Physics, Vol. 113, Issue 18
  • DOI: 10.1063/1.1316043

A theoretical study of small copper oxide clusters: Cu2Ox (x=1–4)
journal, February 2004

  • Dai, Bing; Tian, Li; Yang, Jinlong
  • The Journal of Chemical Physics, Vol. 120, Issue 6
  • DOI: 10.1063/1.1638733

Electronic structure of small copper oxide clusters: From Cu 2 O to Cu 2 O 4
journal, March 1996


Spin-State Energetics of Fe Complexes from an Optimally Tuned Range-Separated Hybrid Functional
journal, December 2017

  • Prokopiou, Georgia; Kronik, Leeor
  • Chemistry - A European Journal, Vol. 24, Issue 20
  • DOI: 10.1002/chem.201704014

Combining GW calculations with exact-exchange density-functional theory: an analysis of valence-band photoemission for compound semiconductors
journal, January 2005


Highest electron affinity as a predictor of cluster anion structures
journal, September 2002

  • Kronik, Leeor; Fromherz, Roland; Ko, Eunjung
  • Nature Materials, Vol. 1, Issue 1
  • DOI: 10.1038/nmat704

Energy-consistent pseudopotentials for group 11 and 12 atoms: adjustment to multi-configuration Dirac–Hartree–Fock data
journal, April 2005


Theoretical Study of the Fe(phen) 2 (NCS) 2 Spin-Crossover Complex with Reparametrized Density Functionals
journal, December 2002


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

Self-interaction correction to density-functional approximations for many-electron systems
journal, May 1981


Cu and Ag as one‐valence‐electron atoms: Pseudopotential CI results for CuO and AgO
journal, September 1984

  • Igel, G.; Wedig, U.; Dolg, M.
  • The Journal of Chemical Physics, Vol. 81, Issue 6
  • DOI: 10.1063/1.447945

Photoelectron spectroscopy of copper oxide (CuO-)
journal, May 1991

  • Polak, Mark L.; Gilles, Mary K.; Ho, Joe
  • The Journal of Physical Chemistry, Vol. 95, Issue 9
  • DOI: 10.1021/j100162a005

Neutral and anionic CuO2: an ab inito study
journal, June 2000


Electronic states of CuO
journal, September 1985

  • Madhavan, P. V.; Newton, M. D.
  • The Journal of Chemical Physics, Vol. 83, Issue 5
  • DOI: 10.1063/1.449327

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/physrevlett.77.3865

Dioxygen activation by photoexcited copper atoms
journal, October 1983

  • Ozin, Geoffrey A.; Mitchell, Steven A.; Garcia-Prieto, Jamie
  • Journal of the American Chemical Society, Vol. 105, Issue 21
  • DOI: 10.1021/ja00359a006

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


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

Systematic Study of Oxo, Peroxo, and Superoxo Isomers of 3d-Metal Dioxides and Their Anions
journal, December 2000

  • Gutsev, G. L.; Rao, B. K.; Jena, P.
  • The Journal of Physical Chemistry A, Vol. 104, Issue 51
  • DOI: 10.1021/jp002252s

Density Functional Calculation of the Structure and Electronic Properties of Cu n O n ( n = 1−8) Clusters
journal, March 2011

  • Bae, Gyun-Tack; Dellinger, Barry; Hall, Randall W.
  • The Journal of Physical Chemistry A, Vol. 115, Issue 11
  • DOI: 10.1021/jp104177q

A theoretical study of the linear OCuO species
journal, July 1999

  • Deng, Ke; Yang, Jinlong; Yuan, Lanfeng
  • The Journal of Chemical Physics, Vol. 111, Issue 4
  • DOI: 10.1063/1.479406

Electronic structure of CoPc adsorbed on Ag(100): Evidence for molecule-substrate interaction mediated by Co 3 d orbitals
journal, February 2013


Density‐functional thermochemistry. IV. A new dynamical correlation functional and implications for exact‐exchange mixing
journal, January 1996

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 104, Issue 3
  • DOI: 10.1063/1.470829

Photodetachment and photodissociation of the linear OCuO molecular anion: energy and time dependence of Cu production
journal, January 2014

  • Mabbs, Richard; Holtgrewe, Nicholas; Dao, Diep Bich
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 2
  • DOI: 10.1039/c3cp52986j

Two isomers of CuO 2 : The Cu(O 2 ) complex and the copper dioxide
journal, September 1995

  • Wu, Hongbin; Desai, Sunil R.; Wang, Lai‐Sheng
  • The Journal of Chemical Physics, Vol. 103, Issue 10
  • DOI: 10.1063/1.470676

Electron correlation and the self-interaction error of density functional theory
journal, June 2002


A density functional study of CuO2 molecules: structural stability, bonding and temperature effects
journal, December 2000


Reactions of Laser-Ablated Copper Atoms with Dioxygen. Infrared Spectra of the Copper Oxides CuO, OCuO, CuOCuO, and OCuOCuO and Superoxide CuOO in Solid Argon
journal, May 1997

  • Chertihin, George V.; Andrews, Lester; Bauschlicher, Charles W.
  • The Journal of Physical Chemistry A, Vol. 101, Issue 22
  • DOI: 10.1021/jp9701653

Experimental and theoretical electronic structure of quinacridone
journal, August 2014


Effect of self-consistency on quasiparticles in solids
journal, July 2006


Excitation Gaps of Finite-Sized Systems from Optimally Tuned Range-Separated Hybrid Functionals
journal, April 2012

  • Kronik, Leeor; Stein, Tamar; Refaely-Abramson, Sivan
  • Journal of Chemical Theory and Computation, Vol. 8, Issue 5
  • DOI: 10.1021/ct2009363

Excitation spectra of aromatic molecules within a real-space G W -BSE formalism: Role of self-consistency and vertex corrections
journal, August 2016


Theoretical study of the X2Π and A2Σ+ states of CUO and CUS
journal, February 1986


Electronic structure of copper phthalocyanine: A comparative density functional theory study
journal, April 2008

  • Marom, Noa; Hod, Oded; Scuseria, Gustavo E.
  • The Journal of Chemical Physics, Vol. 128, Issue 16
  • DOI: 10.1063/1.2898540

Modeling Photoelectron Spectra of CuO, Cu 2 O, and CuO 2 Anions with Equation-of-Motion Coupled-Cluster Methods: An Adventure in Fock Space
journal, December 2017


Structure of copper oxide (CuO2) and its photochemistry in rare gas matrixes
journal, May 1984

  • Bondybey, V. E.; English, J. H.
  • The Journal of Physical Chemistry, Vol. 88, Issue 11
  • DOI: 10.1021/j150655a014

Orbital-dependent density functionals: Theory and applications
journal, January 2008


    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