A parameter-free density functional that works for noncovalent interactions

Hendrik Eshuis, Filipp Furche

Research output: Contribution to journalArticle

103 Citations (Scopus)

Abstract

The failure of semilocal density functional theory for medium- and long-range noncovalent molecular interactions is a long-standing challenge for computational chemistry. Here, we assess the performance of the random phase approximation (RPA), a parameter-free fifth-rung functional, for reaction energies governed by changes in medium- and long-range noncovalent interactions. Our benchmark data include relative energies of alkane isomers, two sets of isomerization reactions testing intramolecular dispersion, a set of dimers of biological importance, a hierarchy of n-homodesmotic reactions, and the predissociation of a ruthenium-based Grubbs catalyst with bulky ligands. The RPA results are an order of magnitude more accurate than those of popular semilocal functionals such as PBE or B3LYP and more systematic than those of semiempirical functionals parametrized for weak interactions, such as B2PLYP-D or M06-2X. In conclusion, RPA is highly promising for thermochemical applications, particularly if noncovalent interactions are important.

Original languageEnglish
Pages (from-to)983-989
Number of pages7
JournalJournal of Physical Chemistry Letters
Volume2
Issue number9
DOIs
StatePublished - 5 May 2011

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Computational chemistry
Alkanes
Ruthenium
Molecular interactions
Isomerization
Isomers
Dimers
Paraffins
Density functional theory
Ligands
Catalysts
Testing

Cite this

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title = "A parameter-free density functional that works for noncovalent interactions",
abstract = "The failure of semilocal density functional theory for medium- and long-range noncovalent molecular interactions is a long-standing challenge for computational chemistry. Here, we assess the performance of the random phase approximation (RPA), a parameter-free fifth-rung functional, for reaction energies governed by changes in medium- and long-range noncovalent interactions. Our benchmark data include relative energies of alkane isomers, two sets of isomerization reactions testing intramolecular dispersion, a set of dimers of biological importance, a hierarchy of n-homodesmotic reactions, and the predissociation of a ruthenium-based Grubbs catalyst with bulky ligands. The RPA results are an order of magnitude more accurate than those of popular semilocal functionals such as PBE or B3LYP and more systematic than those of semiempirical functionals parametrized for weak interactions, such as B2PLYP-D or M06-2X. In conclusion, RPA is highly promising for thermochemical applications, particularly if noncovalent interactions are important.",
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A parameter-free density functional that works for noncovalent interactions. / Eshuis, Hendrik; Furche, Filipp.

In: Journal of Physical Chemistry Letters, Vol. 2, No. 9, 05.05.2011, p. 983-989.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A parameter-free density functional that works for noncovalent interactions

AU - Eshuis, Hendrik

AU - Furche, Filipp

PY - 2011/5/5

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AB - The failure of semilocal density functional theory for medium- and long-range noncovalent molecular interactions is a long-standing challenge for computational chemistry. Here, we assess the performance of the random phase approximation (RPA), a parameter-free fifth-rung functional, for reaction energies governed by changes in medium- and long-range noncovalent interactions. Our benchmark data include relative energies of alkane isomers, two sets of isomerization reactions testing intramolecular dispersion, a set of dimers of biological importance, a hierarchy of n-homodesmotic reactions, and the predissociation of a ruthenium-based Grubbs catalyst with bulky ligands. The RPA results are an order of magnitude more accurate than those of popular semilocal functionals such as PBE or B3LYP and more systematic than those of semiempirical functionals parametrized for weak interactions, such as B2PLYP-D or M06-2X. In conclusion, RPA is highly promising for thermochemical applications, particularly if noncovalent interactions are important.

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