Comparison of the Performance of Density Functional Methods for the Description of Spin States and Binding Energies of Porphyrins

This work analyzes the performance of 250 electronic structure theory methods (including 240 density functional approximations) for the description of spin states and the binding properties of iron, manganese, and cobalt porphyrins. The assessment employs the Por21 database of high-level computational data (CASPT2 reference energies taken from the literature). Results show that current approximations fail to achieve the chemical accuracy target of 1.0 kcal/mol by a long margin. The best-performing methods achieve a mean unsigned error (MUE) <15.0 kcal/mol, but the errors are at least twice as large for most methods. Semilocal functionals and global hybrid functionals with a low percentage of exact exchange are found to be the least problematic for spin states and binding energies, in agreement with the general knowledge in transition metal computational chemistry. Approximations with high percentages of exact exchange (including range-separated and double-hybrid functionals) can lead to catastrophic failures. More modern approximations usually perform better than older functionals. An accurate statistical analysis of the results also casts doubts on some of the reference energies calculated using multireference methods. Suggestions and general guidelines for users are provided in the conclusions. These results hopefully stimulate advances for both the wave function and the density functional side of electronic structure calculations.

Automated summary

This study analyzes the performance of 250 electronic structure theory methods for the description of spin states and binding properties of metal porphyrins. Results show that current approximations fail to achieve the chemical accuracy target and that semilocal and low-exchange hybrid functionals perform better. Approximations with high exchange can lead to catastrophic failures. More modern approximations perform better than older ones. The study also raises doubts on some of the reference energies calculated using multireference methods.