Improved Spin-State Energy Differences of Fe(II) Molecular and Crystalline Complexes via the Hubbard U-Corrected Density
LA Mariano, B Vlaisavljevich… - Journal of Chemical Theory …, 2021 - ACS Publications
Journal of Chemical Theory and Computation, 2021•ACS Publications
We recently showed that the DFT+ U approach with a linear-response U yields adiabatic
energy differences biased toward high spin [Mariano et al. J. Chem. Theory Comput. 2020,
16, 6755–6762]. Such bias is removed here by employing a density-corrected DFT
approach where the PBE functional is evaluated on the Hubbard U-corrected density. The
adiabatic energy differences of six Fe (II) molecular complexes computed using this
approach, named PBE [U] here, are in excellent agreement with coupled cluster-corrected …
energy differences biased toward high spin [Mariano et al. J. Chem. Theory Comput. 2020,
16, 6755–6762]. Such bias is removed here by employing a density-corrected DFT
approach where the PBE functional is evaluated on the Hubbard U-corrected density. The
adiabatic energy differences of six Fe (II) molecular complexes computed using this
approach, named PBE [U] here, are in excellent agreement with coupled cluster-corrected …
We recently showed that the DFT+U approach with a linear-response U yields adiabatic energy differences biased toward high spin [Mariano et al. J. Chem. Theory Comput. 2020, 16, 6755–6762]. Such bias is removed here by employing a density-corrected DFT approach where the PBE functional is evaluated on the Hubbard U-corrected density. The adiabatic energy differences of six Fe(II) molecular complexes computed using this approach, named PBE[U] here, are in excellent agreement with coupled cluster-corrected CASPT2 values for both weak- and strong-field ligands resulting in a mean absolute error (MAE) of 0.44 eV, smaller than that of the recently proposed Hartree–Fock density-corrected DFT (1.22 eV) and any other tested functional, including the best performer TPSSh (0.49 eV). We take advantage of the computational efficiency of this approach and compute the adiabatic energy differences of five molecular crystals using PBE[U] with periodic boundary conditions. The results show, again, an excellent agreement (MAE = 0.07 eV) with experimentally extracted values and a superior performance compared with the best performers M06-L (MAE = 0.08 eV) and TPSSh (MAE = 0.31 eV) computed on molecular fragments.
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