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Title: Effect of Hartree-Fock exact exchange on intramolecular magnetic coupling constants of organic diradicals

The intramolecular magnetic coupling constant (J) of diradical systems linked with five- or six-membered aromatic rings was calculated to obtain the scaling factor (experimental J/calculated J ratio) for various density functional theory (DFT) functionals. Scaling factors of group A (PBE, TPSSh, B3LYP, B97-1, X3LYP, PBE0, and BH and HLYP) and B (M06-L, M06, M06-2X, and M06-HF) were shown to decrease as the amount of Hartree-Fock exact exchange (HFx) increases, in other words, overestimation of calculated J becomes more severe as the HFx increases. We further investigated the effect of HFx fraction of DFT functional on J value, spin contamination, and spin density distributions by comparing the B3LYP analogues containing different amount of HFx. It was revealed that spin contamination and spin densities at each atom increases as the HFx increases. Above all, newly developed BLYP-5 functional, which has 5% of HFx, was found to have the scaling factor of 1.029, indicating that calculated J values are very close to that of experimental values without scaling. BLYP-5 has potential to be utilized for accurate evaluation of intramolecular magnetic coupling constant (J) of diradicals linked by five- or six-membered aromatic ring couplers.
Authors:
; ;  [1] ; ; ;  [2] ;  [2] ;  [3] ;  [3] ;  [4]
  1. Department of Chemistry, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of)
  2. Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555 (Japan)
  3. (Japan)
  4. (ESICB), Kyoto University, Katsura, Kyoto 615-8520 (Japan)
Publication Date:
OSTI Identifier:
22415840
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 2; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AROMATICS; ATOMS; COMPARATIVE EVALUATIONS; COUPLING CONSTANTS; DENSITY FUNCTIONAL METHOD; FUNCTIONALS; HARTREE-FOCK METHOD; MOLECULES; POTENTIALS; RADICALS; SPIN