Global hybrid functionals: A look at the engine under the hood

G. Csonka, John P. Perdew, Adrienn Ruzsinszky

Research output: Contribution to journalArticle

57 Citations (Scopus)

Abstract

Global hybrids, which add a typically modest fraction of the exact exchange energy to a complement of semilocal exchange-correlation energy, are among the most widely used density functionals in chemistry and condensed matter physics. Here we briefly review the formal and practical advantages and disadvantages of global hybrids. We point out that empiricism seems unavoidable in the construction of global hybrids, as it is not for most other kinds of density functional. Then we use one to three parameters to hybridize many semilocal functionals (including recently developed nonempirical generalized gradient approximations or GGA's and meta-GGA's). We study the performance of these global hybrids for many properties of spbonded molecules composed from the lighter atoms of the periodic table: atomization energies, barrier heights, reaction energies, enthalpies of formation, total energies, ionization potentials, electron affinities, proton affinities, and equilibrium bond lengths. We find several new global hybrids that perform better in these tests than standard ones, and we correct some errors in literature assessments. We also discuss the representativity of small fitting sets and the adequacy of various Gaussian basis sets.

Original languageEnglish
Pages (from-to)3688-3703
Number of pages16
JournalJournal of Chemical Theory and Computation
Volume6
Issue number12
DOIs
Publication statusPublished - Dec 14 2010

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Condensed matter physics
Electron affinity
Ionization potential
Energy barriers
Bond length
Atomization
functionals
engines
Protons
Enthalpy
Engines
Atoms
Molecules
condensed matter physics
adequacy
energy
atomizing
electron affinity
ionization potentials
complement

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computer Science Applications

Cite this

Global hybrid functionals : A look at the engine under the hood. / Csonka, G.; Perdew, John P.; Ruzsinszky, Adrienn.

In: Journal of Chemical Theory and Computation, Vol. 6, No. 12, 14.12.2010, p. 3688-3703.

Research output: Contribution to journalArticle

Csonka, G. ; Perdew, John P. ; Ruzsinszky, Adrienn. / Global hybrid functionals : A look at the engine under the hood. In: Journal of Chemical Theory and Computation. 2010 ; Vol. 6, No. 12. pp. 3688-3703.
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