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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

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)
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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 Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1461993
Alternate ID(s):
OSTI ID: 1435669
Journal Information:
Journal of Chemical Physics, Vol. 148, Issue 17; Related Information: © 2018 Author(s).; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 19 works
Citation information provided by
Web of Science

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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

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