Basis set convergence of molecular correlation energy differences within the random phase approximation

Hendrik Eshuis, Filipp Furche

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Abstract

The basis set convergence of energy differences obtained from the random phase approximation (RPA) to the correlation energy is investigated for a wide range of molecular interactions. For dispersion bound systems the basis set incompleteness error is most pronounced, as shown for the S22 benchmark [P. Jurecka, Phys. Chem. Chem. Phys. 8, 1985 (2006)10.1039/b600027d]. The use of very large basis sets ( quintuple-zeta) or extrapolation to the complete basis set (CBS) limit is necessary to obtain a reliable estimate of the binding energy for these systems. Counterpoise corrected results converge to the same CBS limit, but counterpoise correction without extrapolation is insufficient. Core-valence correlations do not play a significant role. For medium- and short-range correlation, quadruple-zeta results are essentially converged, as demonstrated for relative alkane conformer energies, reaction energies dominated by intramolecular dispersion, isomerization energies, and reaction energies of small organic molecules. Except for weakly bound systems, diffuse augmentation almost universally slows down basis set convergence. For most RPA applications, quadruple-zeta valence basis sets offer a good balance between accuracy and efficiency.

Original languageEnglish
Article number084105
JournalJournal of Chemical Physics
Volume136
Issue number8
DOIs
StatePublished - 28 Feb 2012

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Extrapolation
Alkanes
Molecular interactions
Isomerization
Binding energy
approximation
Molecules
energy
extrapolation
valence
molecular interactions
alkanes
isomerization
binding energy
augmentation
estimates
molecules

Cite this

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Basis set convergence of molecular correlation energy differences within the random phase approximation. / Eshuis, Hendrik; Furche, Filipp.

In: Journal of Chemical Physics, Vol. 136, No. 8, 084105, 28.02.2012.

Research output: Contribution to journalArticleResearchpeer-review

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AU - Furche, Filipp

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AB - The basis set convergence of energy differences obtained from the random phase approximation (RPA) to the correlation energy is investigated for a wide range of molecular interactions. For dispersion bound systems the basis set incompleteness error is most pronounced, as shown for the S22 benchmark [P. Jurecka, Phys. Chem. Chem. Phys. 8, 1985 (2006)10.1039/b600027d]. The use of very large basis sets ( quintuple-zeta) or extrapolation to the complete basis set (CBS) limit is necessary to obtain a reliable estimate of the binding energy for these systems. Counterpoise corrected results converge to the same CBS limit, but counterpoise correction without extrapolation is insufficient. Core-valence correlations do not play a significant role. For medium- and short-range correlation, quadruple-zeta results are essentially converged, as demonstrated for relative alkane conformer energies, reaction energies dominated by intramolecular dispersion, isomerization energies, and reaction energies of small organic molecules. Except for weakly bound systems, diffuse augmentation almost universally slows down basis set convergence. For most RPA applications, quadruple-zeta valence basis sets offer a good balance between accuracy and efficiency.

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