A simple DFT-based diagnostic for nondynamical correlation

Uma R. Fogueri; Sebastian Kozuch; Amir Karton; Jan M.L. Martin

doi:10.1007/s00214-012-1291-y

A simple DFT-based diagnostic for nondynamical correlation

Uma R. Fogueri, Sebastian Kozuch, Amir Karton, Jan M.L. Martin

Research output: Contribution to journal › Article › peer-review

61 Scopus citations

Abstract

We propose a simple DFT-based diagnostic for nondynamical correlation effects, namely A_λ = (1 - TAE[X_λC]/TAE[XC])/λ where TAE stands for the molecular total atomization energy, XC is a pure-DFT exchange-correlation functional, and X_λC represents the corresponding hybrid with 100λ % Hartree-Fock-type exchange. The diagnostic is a good predictor for sensitivity of energetics to the level of theory, unlike most wavefunction- based diagnostics. For GGA functionals, A_λ values approaching unity indicate severe nondynamical correlation, while values between 0 and about 0.1 indicate systems where correlation is predominantly dynamical in character (or entirely absent). The diagnostic is only weakly sensitive to the basis set (beyond polarized valence double zeta) and can easily be applied to problems beyond the practical reach of wavefunction ab initio methods required for other diagnostics. We also propose a simple measure for the importance of dynamic correlation.

Original language	English
Pages (from-to)	1-9
Number of pages	9
Journal	Theoretical Chemistry Accounts
Volume	132
Issue number	1
DOIs	https://doi.org/10.1007/s00214-012-1291-y
State	Published - 1 Jan 2013
Externally published	Yes

Keywords

Ab initio
Density functional theory
Diagnostics
Nondynamical correlation
Thermochemistry

ASJC Scopus subject areas

Physical and Theoretical Chemistry

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10.1007/s00214-012-1291-y

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title = "A simple DFT-based diagnostic for nondynamical correlation",

abstract = "We propose a simple DFT-based diagnostic for nondynamical correlation effects, namely Aλ = (1 - TAE[XλC]/TAE[XC])/λ where TAE stands for the molecular total atomization energy, XC is a pure-DFT exchange-correlation functional, and XλC represents the corresponding hybrid with 100λ % Hartree-Fock-type exchange. The diagnostic is a good predictor for sensitivity of energetics to the level of theory, unlike most wavefunction- based diagnostics. For GGA functionals, Aλ values approaching unity indicate severe nondynamical correlation, while values between 0 and about 0.1 indicate systems where correlation is predominantly dynamical in character (or entirely absent). The diagnostic is only weakly sensitive to the basis set (beyond polarized valence double zeta) and can easily be applied to problems beyond the practical reach of wavefunction ab initio methods required for other diagnostics. We also propose a simple measure for the importance of dynamic correlation.",

keywords = "Ab initio, Density functional theory, Diagnostics, Nondynamical correlation, Thermochemistry",

author = "Fogueri, {Uma R.} and Sebastian Kozuch and Amir Karton and Martin, {Jan M.L.}",

note = "Funding Information: J. M. L. M. is on leave of absence as the Thatcher Professor of Chemistry at the Weizmann Institute of Science. This research was supported in part by a startup grant from the University of North Texas from which the Martin group Linux cluster was purchased. U. R. F. acknowledges a research assistant fellowship from the Department of Chemistry at the University of North Texas, while S. K. and A. K. acknowledge Koshland and Australian Research Council postdoctoral fellowships, respectively. The authors would like to thank the reviewers for helpful comments, and Drs. Wanyi Jiang and Angela K. Wilson (U. of North Texas) for helpful discussions. ",

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AU - Fogueri, Uma R.

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AU - Karton, Amir

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N1 - Funding Information: J. M. L. M. is on leave of absence as the Thatcher Professor of Chemistry at the Weizmann Institute of Science. This research was supported in part by a startup grant from the University of North Texas from which the Martin group Linux cluster was purchased. U. R. F. acknowledges a research assistant fellowship from the Department of Chemistry at the University of North Texas, while S. K. and A. K. acknowledge Koshland and Australian Research Council postdoctoral fellowships, respectively. The authors would like to thank the reviewers for helpful comments, and Drs. Wanyi Jiang and Angela K. Wilson (U. of North Texas) for helpful discussions.

PY - 2013/1/1

Y1 - 2013/1/1

N2 - We propose a simple DFT-based diagnostic for nondynamical correlation effects, namely Aλ = (1 - TAE[XλC]/TAE[XC])/λ where TAE stands for the molecular total atomization energy, XC is a pure-DFT exchange-correlation functional, and XλC represents the corresponding hybrid with 100λ % Hartree-Fock-type exchange. The diagnostic is a good predictor for sensitivity of energetics to the level of theory, unlike most wavefunction- based diagnostics. For GGA functionals, Aλ values approaching unity indicate severe nondynamical correlation, while values between 0 and about 0.1 indicate systems where correlation is predominantly dynamical in character (or entirely absent). The diagnostic is only weakly sensitive to the basis set (beyond polarized valence double zeta) and can easily be applied to problems beyond the practical reach of wavefunction ab initio methods required for other diagnostics. We also propose a simple measure for the importance of dynamic correlation.

AB - We propose a simple DFT-based diagnostic for nondynamical correlation effects, namely Aλ = (1 - TAE[XλC]/TAE[XC])/λ where TAE stands for the molecular total atomization energy, XC is a pure-DFT exchange-correlation functional, and XλC represents the corresponding hybrid with 100λ % Hartree-Fock-type exchange. The diagnostic is a good predictor for sensitivity of energetics to the level of theory, unlike most wavefunction- based diagnostics. For GGA functionals, Aλ values approaching unity indicate severe nondynamical correlation, while values between 0 and about 0.1 indicate systems where correlation is predominantly dynamical in character (or entirely absent). The diagnostic is only weakly sensitive to the basis set (beyond polarized valence double zeta) and can easily be applied to problems beyond the practical reach of wavefunction ab initio methods required for other diagnostics. We also propose a simple measure for the importance of dynamic correlation.

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KW - Density functional theory

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KW - Thermochemistry

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A simple DFT-based diagnostic for nondynamical correlation

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