Improved Spin-State Energy Differences of Fe(II) Molecular and Crystalline Complexes via the Hubbard U-Corrected Density

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.

Automated summary

The density-corrected DFT approach named PBE[U] shows excellent agreement in calculating the adiabatic energy differences of Fe(II) molecular complexes and molecular crystals. It outperforms other tested functionals, including the best performer TPSSh, in terms of mean absolute error (MAE). The computational efficiency and accuracy in comparison with experimentally extracted values make it a superior choice for such calculations.