用Hubbard U校正密度改进Fe（II）分子和晶体配合物的自旋态能差
Improved Spin-State Energy Differences of Fe(II) molecular and crystalline complexes via the Hubbard U-corrected Density
摘要：
我们最近表明，具有线性响应U的DFT + U方法产生偏向高自旋的绝热能量差[Mariano等人，J. Chem. Theory Comput. 2020，16，6755 - 6762]。这种偏差在这里通过采用密度校正的DFT方法来去除，其中PBE泛函在Hubbard U校正的密度上进行评估。用这种方法计算的六个Fe（II）分子络合物的绝热能差（PBE [U]）与弱场和强场配体的耦合簇校正CASPT 2值非常一致，平均绝对误差（MAE）为0.44 eV，小于最近提出的Hartree-Fock密度校正DFT（1.22 eV）和任何其他测试功能，包括最佳性能TPSSh（0.49 eV）。我们利用这种方法的计算效率和计算的绝热能量差的五个分子晶体使用PBE [U]与周期性边界条件。结果再次显示，与实验提取的值具有极好的一致性（MAE = 0.07 eV），并且与对分子片段计算的最佳性能TPSSh（MAE = 0.08 eV）和M06-L（MAE = 0.31 eV）相比具有优异的性能。
英文摘要：
We recently showed that the DFT+U approach with a linear-response U yields adiabatic energy differences biased towards 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 here PBE[U], are in excellent agreement with coupled luster-corrected CASPT2 values for both weak- and strong-field ligands resulting in a mean absolute error (MAE) of 0.44 eV, smaller than 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 TPSSh (MAE=0.08 eV) and M06-L (MAE=0.31 eV) computed on molecular fragments.
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