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  • Title: Biased Spin-State Energetics of Fe(II) Molecular Complexes within Density-Functional Theory and the Linear-Response Hubbard U Correction.
    Author: Mariano LA, Vlaisavljevich B, Poloni R.
    Journal: J Chem Theory Comput; 2020 Nov 10; 16(11):6755-6762. PubMed ID: 33108722.
    Abstract:
    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. 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.
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