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Biased Spin-State Energetics of Fe(II) Molecular Complexes within Density-Functional Theory and the Linear-Response Hubbard U Correction

Journal Article · · Journal of Chemical Theory and Computation
 [1];  [2];  [3]
  1. Univ. of Grenoble-Alpes (France); University of South Dakota
  2. Univ. of South Dakota, Vermillion, SD (United States)
  3. Univ. of Grenoble-Alpes (France)
+ Show Author Affiliations
The spin-state energetics of six Fe(II) molecular complexes are computed using the linear-response Hubbard U approach within DFT. The adiabatic energy differences, ΔEH-L, between the high-spin (S = 2) and the low-spin (S = 0) states are computed and compared with accurate-coupled cluster-corrected CASPT2 results. We show that DFT+U fails in correctly capturing the ground state for strong-field ligands yielding ΔEH-L that are almost constant throughout the molecular series. This bias toward high spin together with the metal/ligand charge transfer upon U correction are here quantified and explained using molecular orbital diagrams involving both σ- and π-bonding interactions. Furthermore, with increasing ligand-field strengths this bias also increases owing to the stronger molecular character of the metal/ligand Kohn–Sham orbitals thus resulting in large deviations from the reference larger than 4 eV. Smaller values of U can be employed to mitigate this effect and recover the right energetics.
Research Organization:
Univ. of South Dakota, Vermillion, SD (United States)
Sponsoring Organization:
CINES; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
Grant/Contract Number:
SC0019463; AC02-05CH11231
OSTI ID:
1774499
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 11 Vol. 16; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Improved Spin-State Energy Differences of Fe(II) molecular and crystalline complexes via the Hubbard U-corrected Density preprint January 2021

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Energy
Hybridization
Ligands
Molecular orbitals
Quantum mechanics