Evaluation of the Performance of the B3LYP, PBE0, and M06 DFT Functionals, and DBLOC-Corrected Versions, in the Calculation of Redox Potentials and Spin Splittings for Transition Metal Containing Systems.

Abstract

We have evaluated the performance of the M06 and PBE0 functionals in their ability to calculate spin splittings and redox potentials for octahedral complexes containing a first transition metal series atom. The mean unsigned errors (MUEs) for these two functionals are similar to those obtained for B3LYP using the same data sets. We then apply our localized orbital correction approach for transition metals, DBLOC, in an effort to improve the results obtained with both functionals. The PBE0-DBLOC results are remarkably close in both MUE and parameter values to those obtained for the B3LYP-DBLOC method. The M06-DBLOC results are less accurate, but the parameter values and trends are still qualitatively very similar. These results demonstrate that DBLOC corrected methods are substantially more accurate for these systems than any of the uncorrected functionals we have tested and that the deviations between hybrid DFT methods and experiment for transition metal containing systems exhibit striking physically based regularities which are very similar for the three functionals that we have examined, despite significant differences in the details of each model.