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

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

Journal Article · · Journal of Chemical Physics
DOI: https://doi.org/10.1063/1.5031027 · OSTI ID:1461993
ORCiD logo [1]; ORCiD logo [2]
  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)
+ Show Author Affiliations

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.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1461993
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 17 Vol. 148; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

References (37)

Double-hybrid density functionals: Double-hybrid density functionals journal July 2014
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
Self-interaction error of local density functionals for alkali–halide dissociation journal April 2006
How Accurate Is Density Functional Theory at Predicting Dipole Moments? An Assessment Using a New Database of 200 Benchmark Values journal March 2018
Is the Accuracy of Density Functional Theory for Atomization Energies and Densities in Bonding Regions Correlated? journal April 2017
Challenges for Density Functional Theory journal December 2011
Assessment of Orbital-Optimized, Spin-Component Scaled Second-Order Many-Body Perturbation Theory for Thermochemistry and Kinetics journal October 2009
Fractional Charge Behavior and Band Gap Predictions with the XYG3 Type of Doubly Hybrid Density Functionals journal June 2014
Highly Accurate First-Principles Benchmark Data Sets for the Parametrization and Validation of Density Functional and Other Approximate Methods. Derivation of a Robust, Generally Applicable, Double-Hybrid Functional for Thermochemistry and Thermochemical Kinetics † journal December 2008
Beyond energies: geometry predictions with the XYG3 type of doubly hybrid density functionals journal January 2016
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
Second-order perturbation corrections to singles and doubles coupled-cluster methods: General theory and application to the valence optimized doubles model journal September 2000
A second-order perturbative correction to the coupled-cluster singles and doubles method: CCSD(2) journal August 2001
Jacob’s ladder of density functional approximations for the exchange-correlation energy conference January 2001
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
The spin–flip approach within time-dependent density functional theory: Theory and applications to diradicals journal March 2003
Semiempirical hybrid density functional with perturbative second-order correlation journal January 2006
Spurious fractional charge on dissociated atoms: Pervasive and resilient self-interaction error of common density functionals journal November 2006
Orbital-optimized opposite-spin scaled second-order correlation: An economical method to improve the description of open-shell molecules journal April 2007
On the evaluation of analytic energy derivatives for correlated wave functions journal December 1984
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Gaussian basis sets for use in correlated molecular calculations. V. Core‐valence basis sets for boron through neon journal September 1995
Orbital optimized double-hybrid density functionals journal July 2013
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
Doubly hybrid density functional for accurate descriptions of nonbond interactions, thermochemistry, and thermochemical kinetics journal March 2009
A fast doubly hybrid density functional method close to chemical accuracy using a local opposite spin ansatz journal November 2011
Violations of N-representability from spin-unrestricted orbitals in Møller–Plesset perturbation theory and related double-hybrid density functional theory journal April 2009
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package journal September 2014
Thirty years of density functional theory in computational chemistry: an overview and extensive assessment of 200 density functionals journal April 2017
XXXIV. Notes on the molecular orbital treatment of the hydrogen molecule journal April 1949
Self-Consistent Equations Including Exchange and Correlation Effects journal November 1965
Density-functional exchange-energy approximation with correct asymptotic behavior journal September 1988
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal January 1988
Density functional theory: Its origins, rise to prominence, and future journal August 2015
Density functional theory is straying from the path toward the exact functional journal January 2017
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density text January 1988

Cited By (7)

How accurate are static polarizability predictions from density functional theory? An assessment over 132 species at equilibrium geometry journal January 2018
Statistically representative databases for density functional theory via data science journal January 2019
Beyond the Coulson–Fischer point: characterizing single excitation CI and TDDFT for excited states in single bond dissociations journal January 2019
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
Rethinking CO adsorption on transition-metal surfaces: Effect of density-driven self-interaction errors journal July 2019
Well-behaved versus ill-behaved density functionals for single bond dissociation: Separating success from disaster functional by functional for stretched H$_2$ text January 2018
Beyond the Coulson-Fischer point: Characterizing single excitation CI and TDDFT for excited states in single bond dissociations text January 2019

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY