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

Title: On the accuracy of density functional theory and wave function methods for calculating vertical ionization energies

Abstract

In this work, the best practice in computational methods for determining vertical ionization energies (VIEs) is assessed, via reference to experimentally determined VIEs that are corroborated by highly accurate coupled-cluster calculations. These reference values are used to benchmark the performance of density-functional theory (DFT) and wave function methods: Hartree-Fock theory (HF), second-order Møller-Plesset perturbation theory (MP2) and Electron Propagator Theory (EPT). The core test set consists of 147 small molecules. An extended set of six larger molecules, from benzene to hexacene, is also considered to investigate the dependence of the results on molecule size. The closest agreement with experiment is found for ionization energies obtained from total energy diff calculations. In particular, DFT calculations using exchange-correlation functionals with either a large amount of exact exchange or long-range correction perform best. The results from these functionals are also the least sensitive to an increase in molecule size. In general, ionization energies calculated directly from the orbital energies of the neutral species are less accurate and more sensitive to an increase in molecule size. For the single-calculation approach, the EPT calculations are in closest agreement for both sets of molecules. For the orbital energies from DFT functionals, only those with long-range correctionmore » give quantitative agreement with dramatic failing for all other functionals considered. The results offer a practical hierarchy of approximations for the calculation of vertical ionization energies. In addition, the experimental and computational reference values can be used as a standardized set of benchmarks, against which other approximate methods can be compared.« less

Authors:
 [1];  [2];  [3];  [4]
+ Show Author Affiliations
  1. Univ. of Cambridge (United Kingdom). Cavendish Lab.
  2. King’s College London, (United Kingdom). Theory and Simulation of Condensed Matter
  3. Univ. of Cambridge (United Kingdom)
  4. Univ. of Cambridge (United Kingdom). Cavendish Lab.; Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; Engineering and Physical Sciences Research Council (EPSRC)
OSTI Identifier:
1391934
Alternate Identifier(s):
OSTI ID: 1228252
Grant/Contract Number:  
AC02-06CH11357; EP/P505445/1
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 142; Journal Issue: 19; 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

McKechnie, Scott, Booth, George H., Cohen, Aron J., and Cole, Jacqueline M. On the accuracy of density functional theory and wave function methods for calculating vertical ionization energies. United States: N. p., 2015. Web. doi:10.1063/1.4921037.
Copy to clipboard
McKechnie, Scott, Booth, George H., Cohen, Aron J., & Cole, Jacqueline M. On the accuracy of density functional theory and wave function methods for calculating vertical ionization energies. United States. https://doi.org/10.1063/1.4921037
Copy to clipboard
McKechnie, Scott, Booth, George H., Cohen, Aron J., and Cole, Jacqueline M. Thu . "On the accuracy of density functional theory and wave function methods for calculating vertical ionization energies". United States. https://doi.org/10.1063/1.4921037. https://www.osti.gov/servlets/purl/1391934.
Copy to clipboard
@article{osti_1391934,
title = {On the accuracy of density functional theory and wave function methods for calculating vertical ionization energies},
author = {McKechnie, Scott and Booth, George H. and Cohen, Aron J. and Cole, Jacqueline M.},
abstractNote = {In this work, the best practice in computational methods for determining vertical ionization energies (VIEs) is assessed, via reference to experimentally determined VIEs that are corroborated by highly accurate coupled-cluster calculations. These reference values are used to benchmark the performance of density-functional theory (DFT) and wave function methods: Hartree-Fock theory (HF), second-order Møller-Plesset perturbation theory (MP2) and Electron Propagator Theory (EPT). The core test set consists of 147 small molecules. An extended set of six larger molecules, from benzene to hexacene, is also considered to investigate the dependence of the results on molecule size. The closest agreement with experiment is found for ionization energies obtained from total energy diff calculations. In particular, DFT calculations using exchange-correlation functionals with either a large amount of exact exchange or long-range correction perform best. The results from these functionals are also the least sensitive to an increase in molecule size. In general, ionization energies calculated directly from the orbital energies of the neutral species are less accurate and more sensitive to an increase in molecule size. For the single-calculation approach, the EPT calculations are in closest agreement for both sets of molecules. For the orbital energies from DFT functionals, only those with long-range correction give quantitative agreement with dramatic failing for all other functionals considered. The results offer a practical hierarchy of approximations for the calculation of vertical ionization energies. In addition, the experimental and computational reference values can be used as a standardized set of benchmarks, against which other approximate methods can be compared.},
doi = {10.1063/1.4921037},
journal = {Journal of Chemical Physics},
number = 19,
volume = 142,
place = {United States},
year = {Thu May 21 00:00:00 EDT 2015},
month = {Thu May 21 00:00:00 EDT 2015}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1063/1.4921037
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 41 works
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:

CurlySMILES: a chemical language to customize and annotate encodings of molecular and nanodevice structures
journal, January 2011

Systematic optimization of long-range corrected hybrid density functionals
journal, February 2008

  • Chai, Jeng-Da; Head-Gordon, Martin
  • The Journal of Chemical Physics, Vol. 128, Issue 8
  • DOI: 10.1063/1.2834918

An efficient reformulation of the closed‐shell coupled cluster single and double excitation (CCSD) equations
journal, December 1988

  • Scuseria, Gustavo E.; Janssen, Curtis L.; Schaefer, Henry F.
  • The Journal of Chemical Physics, Vol. 89, Issue 12
  • DOI: 10.1063/1.455269

A long-range-corrected time-dependent density functional theory
journal, May 2004

  • Tawada, Yoshihiro; Tsuneda, Takao; Yanagisawa, Susumu
  • The Journal of Chemical Physics, Vol. 120, Issue 18
  • DOI: 10.1063/1.1688752

Is coupled cluster singles and doubles (CCSD) more computationally intensive than quadratic configuration interaction (QCISD)?
journal, April 1989

  • Scuseria, Gustavo E.; Schaefer, Henry F.
  • The Journal of Chemical Physics, Vol. 90, Issue 7
  • DOI: 10.1063/1.455827

A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples
journal, February 1982

  • Purvis, George D.; Bartlett, Rodney J.
  • The Journal of Chemical Physics, Vol. 76, Issue 4
  • DOI: 10.1063/1.443164

Improving Band Gap Prediction in Density Functional Theory from Molecules to Solids
journal, July 2011

A non-Dyson third-order approximation scheme for the electron propagator
journal, September 1998

  • Schirmer, J.; Trofimov, A. B.; Stelter, G.
  • The Journal of Chemical Physics, Vol. 109, Issue 12
  • DOI: 10.1063/1.477085

Density-Functional Theory for Fractional Particle Number: Derivative Discontinuities of the Energy
journal, December 1982

Practical Aspects of Computational Chemistry III
book, January 2014

Long-range corrected functionals satisfy Koopmans' theorem: Calculation of correlation and relaxation energies
journal, January 2013

  • Kar, Rahul; Song, Jong-Won; Hirao, Kimihiko
  • Journal of Computational Chemistry, Vol. 34, Issue 11
  • DOI: 10.1002/jcc.23222

Long-range corrected hybrid meta-generalized-gradient approximations with dispersion corrections
journal, April 2012

  • Lin, You-Sheng; Tsai, Chen-Wei; Li, Guan-De
  • The Journal of Chemical Physics, Vol. 136, Issue 15
  • DOI: 10.1063/1.4704370

Jahn-Teller Effects in Molecular Cations Studied by Photoelectron Spectroscopy and Group Theory
journal, August 2009

  • Wörner, Hans Jakob; Merkt, Frédéric
  • Angewandte Chemie International Edition, Vol. 48, Issue 35
  • DOI: 10.1002/anie.200900526

How to determine vertical ionization potentials from photoelectron spectra
journal, January 1975

A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP)
journal, July 2004

  • Yanai, Takeshi; Tew, David P.; Handy, Nicholas C.
  • Chemical Physics Letters, Vol. 393, Issue 1-3, p. 51-57
  • DOI: 10.1016/j.cplett.2004.06.011

Insights into Current Limitations of Density Functional Theory
journal, August 2008

Assessment of density functional methods with correct asymptotic behavior
text, January 2012

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Derivative discontinuity, bandgap and lowest unoccupied molecular orbital in density functional theory
journal, May 2012

  • Yang, Weitao; Cohen, Aron J.; Mori-Sánchez, Paula
  • The Journal of Chemical Physics, Vol. 136, Issue 20
  • DOI: 10.1063/1.3702391

Assessment of density functional methods with correct asymptotic behavior
journal, January 2013

  • Tsai, Chen-Wei; Su, Yu-Chuan; Li, Guan-De
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 21
  • DOI: 10.1039/c3cp50441g

Many-Body Perturbation Theory and Coupled Cluster Theory for Electron Correlation in Molecules
journal, October 1981

Handbook of Computational Chemistry
book, January 2016

The Kohn–Sham gap, the fundamental gap and the optical gap: the physical meaning of occupied and virtual Kohn–Sham orbital energies
journal, January 2013

  • Baerends, E. J.; Gritsenko, O. V.; van Meer, R.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 39
  • DOI: 10.1039/c3cp52547c

Extension of many-body theory and approximate density functionals to fractional charges and fractional spins
journal, September 2013

  • Yang, Weitao; Mori-Sánchez, Paula; Cohen, Aron J.
  • The Journal of Chemical Physics, Vol. 139, Issue 10
  • DOI: 10.1063/1.4817183

A long-range correction scheme for generalized-gradient-approximation exchange functionals
journal, August 2001

  • Iikura, Hisayoshi; Tsuneda, Takao; Yanai, Takeshi
  • The Journal of Chemical Physics, Vol. 115, Issue 8
  • DOI: 10.1063/1.1383587

Fractional charge perspective on the band-gap in density-functional theory
text, January 2007

Vertical Ionization Energies of Free Radicals and Electron Detachment Energies of Their Anions: A Comparison of Direct and Indirect Methods Versus Experiment
journal, July 2014

  • Pérez-González, Adriana; Galano, Annia; Ortiz, J. V.
  • The Journal of Physical Chemistry A, Vol. 118, Issue 31
  • DOI: 10.1021/jp505276n

Combining long-range configuration interaction with short-range density functionals
journal, August 1997

Challenges for Density Functional Theory
journal, December 2011

  • Cohen, Aron J.; Mori-Sánchez, Paula; Yang, Weitao
  • Chemical Reviews, Vol. 112, Issue 1
  • DOI: 10.1021/cr200107z

Tests of functionals for systems with fractional electron number
journal, April 2007

  • Vydrov, Oleg A.; Scuseria, Gustavo E.; Perdew, John P.
  • The Journal of Chemical Physics, Vol. 126, Issue 15
  • DOI: 10.1063/1.2723119

Benchmark theoretical study of the ionization threshold of benzene and oligoacenes
journal, August 2003

  • Deleuze, M. S.; Claes, L.; Kryachko, E. S.
  • The Journal of Chemical Physics, Vol. 119, Issue 6
  • DOI: 10.1063/1.1589731

Orbital energies and Koopmans' theorem in open-shell Hartree-Fock theory
journal, February 1972

On Koopmans’ theorem in density functional theory
journal, November 2010

  • Tsuneda, Takao; Song, Jong-Won; Suzuki, Satoshi
  • The Journal of Chemical Physics, Vol. 133, Issue 17
  • DOI: 10.1063/1.3491272

Interpretation of the Kohn–Sham orbital energies as approximate vertical ionization potentials
journal, February 2002

  • Chong, D. P.; Gritsenko, O. V.; Baerends, E. J.
  • The Journal of Chemical Physics, Vol. 116, Issue 5
  • DOI: 10.1063/1.1430255

Localization and Delocalization Errors in Density Functional Theory and Implications for Band-Gap Prediction
journal, April 2008

Many-electron self-interaction error in approximate density functionals
journal, November 2006

  • Mori-Sánchez, Paula; Cohen, Aron J.; Yang, Weitao
  • The Journal of Chemical Physics, Vol. 125, Issue 20
  • DOI: 10.1063/1.2403848

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

Ionization Potential, Electron Affinity, Electronegativity, Hardness, and Electron Excitation Energy:  Molecular Properties from Density Functional Theory Orbital Energies
journal, May 2003

  • Zhan, Chang-Guo; Nichols, Jeffrey A.; Dixon, David A.
  • The Journal of Physical Chemistry A, Vol. 107, Issue 20
  • DOI: 10.1021/jp0225774

Application and Testing of Diagonal, Partial Third-Order Electron Propagator Approximations
book, January 2001

  • Ferreira, Antonio M.; Seabra, Gustavo; Dolgounitcheva, O.
  • Understanding Chemical Reactivity
  • DOI: 10.1007/0-306-47632-0_5

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

Koopmans’ theorem in the ROHF method: Canonical form for the Hartree-Fock Hamiltonian
journal, November 2006

  • Plakhutin, B. N.; Gorelik, E. V.; Breslavskaya, N. N.
  • The Journal of Chemical Physics, Vol. 125, Issue 20
  • DOI: 10.1063/1.2393223

Note on an Approximation Treatment for Many-Electron Systems
journal, October 1934

More π Electrons Make a Difference: Emergence of Many Radicals on Graphene Nanoribbons Studied by Ab Initio DMRG Theory
journal, December 2012

  • Mizukami, Wataru; Kurashige, Yuki; Yanai, Takeshi
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 1
  • DOI: 10.1021/ct3008974

Computational methods for the one-particle green's function
journal, April 1984

Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994

  • Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.
  • The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627
  • DOI: 10.1021/j100096a001

Improving the Accuracy of Hybrid Meta-GGA Density Functionals by Range Separation
journal, October 2011

  • Peverati, Roberto; Truhlar, Donald G.
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 21
  • DOI: 10.1021/jz201170d

Electron propagator theory: an approach to prediction and interpretation in quantum chemistry: Electron propagator theory
journal, September 2012

  • Ortiz, Joseph Vincent
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 3, Issue 2
  • DOI: 10.1002/wcms.1116
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Assignment of photoelectron spectra of intramolecular silicon complexes: 1-vinyl- and 1-phenylsilatranes
    journal, January 2018

    • Belogolova, Elena F.; Doronina, Evgeniya P.; Sidorkin, Valery F.
    • Physical Chemistry Chemical Physics, Vol. 20, Issue 41
    • DOI: 10.1039/c8cp04582h

    Polypyrrole derivatives for optoelectronic applications: a DFT study on the influence of side groups
    journal, January 2019

    • Coleone, Alex Pifer; Lascane, Leonardo Gois; Batagin-Neto, Augusto
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 32
    • DOI: 10.1039/c9cp02638j

    Accurate density functional prediction of molecular electron affinity with the scaling corrected Kohn–Sham frontier orbital energies
    journal, October 2017

    Micropollutant Oxidation Studied by Quantum Chemical Computations: Methodology and Applications to Thermodynamics, Kinetics, and Reaction Mechanisms
    journal, March 2019

    The LDA-1/2 method applied to atoms and molecules
    text, January 2018

      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: