A simple DFT-based diagnostic for nondynamical correlation

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

Research output: Contribution to journalArticlepeer-review

61 Scopus citations

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.

Original languageEnglish
Pages (from-to)1-9
Number of pages9
JournalTheoretical Chemistry Accounts
Volume132
Issue number1
DOIs
StatePublished - 1 Jan 2013
Externally publishedYes

Keywords

  • Ab initio
  • Density functional theory
  • Diagnostics
  • Nondynamical correlation
  • Thermochemistry

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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