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Title: Communication: xDH double hybrid functionals can be qualitatively incorrect for non-equilibrium geometries: Dipole moment inversion and barriers to radical-radical association using XYG3 and XYGJ-OS

Abstract

Here, double hybrid (DH) density functionals are amongst the most accurate density functional approximations developed so far, largely due to the incorporation of correlation effects from unoccupied orbitals via second order perturbation theory (PT2). The xDH family of DH functionals calculate energy directly from orbitals optimized by a lower level approach like B3LYP, without self-consistent optimization. XYG3 and XYGJ-OS are two widely used xDH functionals that are known to be quite accurate at equilibrium geometries. Here, we show that the XYG3 and XYGJ-OS functionals can be ill behaved for stretched bonds well beyond the Coulson-Fischer point, predicting unphysical dipole moments and humps in potential energy curves for some simple systems like the hydrogen fluoride molecule. Numerical experiments and analysis show that these failures are not due to PT2. Instead, a large mismatch at stretched bond-lengths between the reference B3LYP orbitals and the optimized orbitals associated with the non-PT2 part of XYG3 leads to an unphysically large non-Hellman-Feynman contribution to first order properties like forces and electron densities.

Authors:
ORCiD logo [1]; ORCiD logo [2]
+ Show Author Affiliations
  1. Univ. of California, Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1461993
Alternate Identifier(s):
OSTI ID: 1435669
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 17; Related Information: © 2018 Author(s).; 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

Hait, Diptarka, and Head-Gordon, Martin. Communication: xDH double hybrid functionals can be qualitatively incorrect for non-equilibrium geometries: Dipole moment inversion and barriers to radical-radical association using XYG3 and XYGJ-OS. United States: N. p., 2018. Web. doi:10.1063/1.5031027.
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Hait, Diptarka, & Head-Gordon, Martin. Communication: xDH double hybrid functionals can be qualitatively incorrect for non-equilibrium geometries: Dipole moment inversion and barriers to radical-radical association using XYG3 and XYGJ-OS. United States. https://doi.org/10.1063/1.5031027
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Hait, Diptarka, and Head-Gordon, Martin. Wed . "Communication: xDH double hybrid functionals can be qualitatively incorrect for non-equilibrium geometries: Dipole moment inversion and barriers to radical-radical association using XYG3 and XYGJ-OS". United States. https://doi.org/10.1063/1.5031027. https://www.osti.gov/servlets/purl/1461993.
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@article{osti_1461993,
title = {Communication: xDH double hybrid functionals can be qualitatively incorrect for non-equilibrium geometries: Dipole moment inversion and barriers to radical-radical association using XYG3 and XYGJ-OS},
author = {Hait, Diptarka and Head-Gordon, Martin},
abstractNote = {Here, double hybrid (DH) density functionals are amongst the most accurate density functional approximations developed so far, largely due to the incorporation of correlation effects from unoccupied orbitals via second order perturbation theory (PT2). The xDH family of DH functionals calculate energy directly from orbitals optimized by a lower level approach like B3LYP, without self-consistent optimization. XYG3 and XYGJ-OS are two widely used xDH functionals that are known to be quite accurate at equilibrium geometries. Here, we show that the XYG3 and XYGJ-OS functionals can be ill behaved for stretched bonds well beyond the Coulson-Fischer point, predicting unphysical dipole moments and humps in potential energy curves for some simple systems like the hydrogen fluoride molecule. Numerical experiments and analysis show that these failures are not due to PT2. Instead, a large mismatch at stretched bond-lengths between the reference B3LYP orbitals and the optimized orbitals associated with the non-PT2 part of XYG3 leads to an unphysically large non-Hellman-Feynman contribution to first order properties like forces and electron densities.},
doi = {10.1063/1.5031027},
journal = {Journal of Chemical Physics},
number = 17,
volume = 148,
place = {United States},
year = {2018},
month = {5}
}
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https://doi.org/10.1063/1.5031027
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Works referenced in this record:

Thirty years of density functional theory in computational chemistry: an overview and extensive assessment of 200 density functionals
journal, April 2017

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

A look at the density functional theory zoo with the advanced GMTKN55 database for general main group thermochemistry, kinetics and noncovalent interactions
journal, January 2017

  • Goerigk, Lars; Hansen, Andreas; Bauer, Christoph
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 48
  • DOI: 10.1039/c7cp04913g

Spurious fractional charge on dissociated atoms: Pervasive and resilient self-interaction error of common density functionals
journal, November 2006

  • Ruzsinszky, Adrienn; Perdew, John P.; Csonka, Gábor I.
  • The Journal of Chemical Physics, Vol. 125, Issue 19
  • DOI: 10.1063/1.2387954

Self-interaction error of local density functionals for alkali–halide dissociation
journal, April 2006

Semiempirical hybrid density functional with perturbative second-order correlation
journal, January 2006

  • Grimme, Stefan
  • The Journal of Chemical Physics, Vol. 124, Issue 3
  • DOI: 10.1063/1.2148954

Gaussian basis sets for use in correlated molecular calculations. VII. Valence, core-valence, and scalar relativistic basis sets for Li, Be, Na, and Mg
journal, May 2010

  • Prascher, Brian P.; Woon, David E.; Peterson, Kirk A.
  • Theoretical Chemistry Accounts, Vol. 128, Issue 1
  • DOI: 10.1007/s00214-010-0764-0

A second-order perturbative correction to the coupled-cluster singles and doubles method: CCSD(2)
journal, August 2001

  • Gwaltney, Steven R.; Head-Gordon, Martin
  • The Journal of Chemical Physics, Vol. 115, Issue 5
  • DOI: 10.1063/1.1383589

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

Density functional theory: Its origins, rise to prominence, and future
journal, August 2015

Gaussian basis sets for use in correlated molecular calculations. V. Core‐valence basis sets for boron through neon
journal, September 1995

  • Woon, David E.; Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 103, Issue 11
  • DOI: 10.1063/1.470645

Fractional Charge Behavior and Band Gap Predictions with the XYG3 Type of Doubly Hybrid Density Functionals
journal, June 2014

  • Su, Neil Qiang; Yang, Weitao; Mori-Sánchez, Paula
  • The Journal of Physical Chemistry A, Vol. 118, Issue 39
  • DOI: 10.1021/jp5029992

On the evaluation of analytic energy derivatives for correlated wave functions
journal, December 1984

  • Handy, Nicholas C.; Schaefer, Henry F.
  • The Journal of Chemical Physics, Vol. 81, Issue 11
  • DOI: 10.1063/1.447489

Orbital optimized double-hybrid density functionals
journal, July 2013

  • Peverati, Roberto; Head-Gordon, Martin
  • The Journal of Chemical Physics, Vol. 139, Issue 2
  • DOI: 10.1063/1.4812689

Jacob’s ladder of density functional approximations for the exchange-correlation energy
conference, January 2001

  • Perdew, John P.
  • Density functional theory and its application to materials, AIP Conference Proceedings
  • DOI: 10.1063/1.1390175

Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989

  • Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 90, Issue 2
  • DOI: 10.1063/1.456153

The spin–flip approach within time-dependent density functional theory: Theory and applications to diradicals
journal, March 2003

  • Shao, Yihan; Head-Gordon, Martin; Krylov, Anna I.
  • The Journal of Chemical Physics, Vol. 118, Issue 11
  • DOI: 10.1063/1.1545679

Accurate correlation consistent basis sets for molecular core–valence correlation effects: The second row atoms Al–Ar, and the first row atoms B–Ne revisited
journal, December 2002

  • Peterson, Kirk A.; Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 117, Issue 23
  • DOI: 10.1063/1.1520138

Double-hybrid density functionals: Double-hybrid density functionals
journal, July 2014

  • Goerigk, Lars; Grimme, Stefan
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 4, Issue 6
  • DOI: 10.1002/wcms.1193

Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988

How Accurate Is Density Functional Theory at Predicting Dipole Moments? An Assessment Using a New Database of 200 Benchmark Values
journal, March 2018

  • Hait, Diptarka; Head-Gordon, Martin
  • Journal of Chemical Theory and Computation, Vol. 14, Issue 4
  • DOI: 10.1021/acs.jctc.7b01252

Orbital-optimized opposite-spin scaled second-order correlation: An economical method to improve the description of open-shell molecules
journal, April 2007

  • Lochan, Rohini C.; Head-Gordon, Martin
  • The Journal of Chemical Physics, Vol. 126, Issue 16
  • DOI: 10.1063/1.2718952

Comment on “Doubly hybrid density functional xDH-PBE0 from a parameter-free global hybrid model PBE0” [J. Chem. Phys. 136, 174103 (2012)]
journal, November 2015

  • Kesharwani, Manoj K.; Kozuch, Sebastian; Martin, Jan M. L.
  • The Journal of Chemical Physics, Vol. 143, Issue 18
  • DOI: 10.1063/1.4934819

XXXIV. Notes on the molecular orbital treatment of the hydrogen molecule
journal, April 1949

  • Coulson, C. A.; Fischer, I.
  • The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science, Vol. 40, Issue 303
  • DOI: 10.1080/14786444908521726

Density functional theory is straying from the path toward the exact functional
journal, January 2017

  • Medvedev, Michael G.; Bushmarinov, Ivan S.; Sun, Jianwei
  • Science, Vol. 355, Issue 6320
  • DOI: 10.1126/science.aah5975

Is the Accuracy of Density Functional Theory for Atomization Energies and Densities in Bonding Regions Correlated?
journal, April 2017

  • Brorsen, Kurt R.; Yang, Yang; Pak, Michael V.
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 9
  • DOI: 10.1021/acs.jpclett.7b00774

Doubly hybrid density functional for accurate descriptions of nonbond interactions, thermochemistry, and thermochemical kinetics
journal, March 2009

  • Zhang, Y.; Xu, X.; Goddard, W. A.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 13
  • DOI: 10.1073/pnas.0901093106

Assessment of Orbital-Optimized, Spin-Component Scaled Second-Order Many-Body Perturbation Theory for Thermochemistry and Kinetics
journal, October 2009

  • Neese, Frank; Schwabe, Tobias; Kossmann, Simone
  • Journal of Chemical Theory and Computation, Vol. 5, Issue 11
  • DOI: 10.1021/ct9003299

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package
journal, September 2014

A fast doubly hybrid density functional method close to chemical accuracy using a local opposite spin ansatz
journal, November 2011

  • Zhang, I. Y.; Xu, X.; Jung, Y.
  • Proceedings of the National Academy of Sciences, Vol. 108, Issue 50
  • DOI: 10.1073/pnas.1115123108

Second-order perturbation corrections to singles and doubles coupled-cluster methods: General theory and application to the valence optimized doubles model
journal, September 2000

  • Gwaltney, Steven R.; Sherrill, C. David; Head-Gordon, Martin
  • The Journal of Chemical Physics, Vol. 113, Issue 9
  • DOI: 10.1063/1.1286597

Beyond energies: geometry predictions with the XYG3 type of doubly hybrid density functionals
journal, January 2016

  • Su, Neil Qiang; Xu, Xin
  • Chemical Communications, Vol. 52, Issue 96
  • DOI: 10.1039/c6cc04886b

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988

Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
text, January 1988

  • Robert, Parr,; Chengteh, Lee,; Weitao, Yang,
  • The University of North Carolina at Chapel Hill University Libraries
  • DOI: 10.17615/zrp0-ry04
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    journal, January 2018

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    • Physical Chemistry Chemical Physics, Vol. 20, Issue 30
    • DOI: 10.1039/c8cp03569e

    Statistically representative databases for density functional theory via data science
    journal, January 2019

    • Morgante, Pierpaolo; Peverati, Roberto
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 35
    • DOI: 10.1039/c9cp03211h

    Beyond the Coulson–Fischer point: characterizing single excitation CI and TDDFT for excited states in single bond dissociations
    journal, January 2019

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    • Physical Chemistry Chemical Physics, Vol. 21, Issue 39
    • DOI: 10.1039/c9cp04452c

    Well-behaved versus ill-behaved density functionals for single bond dissociation: Separating success from disaster functional by functional for stretched H 2
    journal, March 2019

    • Hait, Diptarka; Rettig, Adam; Head-Gordon, Martin
    • The Journal of Chemical Physics, Vol. 150, Issue 9
    • DOI: 10.1063/1.5080122

    Rethinking CO adsorption on transition-metal surfaces: Effect of density-driven self-interaction errors
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