A comparative study of the singlet-triplet energy separation of carbenes using density functional theory and coupled-cluster methods

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Abstract

The singlet-triplet energy separation (ΔES-T) of carbenes has been studied using density functional theory (DFT) and the single, double, plus perturbative triple excitations coupled-cluster {CCSD(T)} approaches. ΔES-T predictions from DFT were compared with those of CCSD(T). We found that BLYP and G96LYP predictions are closest to the CCSD(T) results, with the average absolute deviations within 1 kcal/mol. Many of the tested functionals overestimate ΔES-T. It was observed that best comparisons are displayed by the choice of correlation (LYP) functionals, while the effect of choosing among exchange functionals is less significant. The hybrid functionals provide poorer, overestimated predictions for ΔES-T.

Original languageEnglish
Pages (from-to)81-89
Number of pages9
JournalChemical Physics Letters
Volume309
Issue number1-2
DOIs
Publication statusPublished - 1999 Aug 6

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carbenes
functionals
Density functional theory
density functional theory
predictions
energy
deviation
carbene
excitation

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

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title = "A comparative study of the singlet-triplet energy separation of carbenes using density functional theory and coupled-cluster methods",
abstract = "The singlet-triplet energy separation (ΔES-T) of carbenes has been studied using density functional theory (DFT) and the single, double, plus perturbative triple excitations coupled-cluster {CCSD(T)} approaches. ΔES-T predictions from DFT were compared with those of CCSD(T). We found that BLYP and G96LYP predictions are closest to the CCSD(T) results, with the average absolute deviations within 1 kcal/mol. Many of the tested functionals overestimate ΔES-T. It was observed that best comparisons are displayed by the choice of correlation (LYP) functionals, while the effect of choosing among exchange functionals is less significant. The hybrid functionals provide poorer, overestimated predictions for ΔES-T.",
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