An isomeric reaction benchmark set to test if the performance of state-of-the-art density functionals can be regarded as independent of the external potential

Abstract

Some representative density functionals are assessed for isomerization reactions in which heteroatoms are systematically substituted with heavier members of the same element group. By this, it is investigated if the functional performance depends on the elements involved, i.e. on the external potential imposed by the atomic nuclei. Special emphasis is placed on reliable theoretical reference data and the attempt to minimize basis set effects. Both issues are challenging for molecules including heavy elements. The data suggest that no general bias can be identified for the functionals under investigation except for one case – M11-L. Nevertheless, large deviations from the reference data can be found for all functional approximations in some cases. The average error range for the nine functionals in this test is 17.6 kcal mol⁻¹. These outliers depreciate the general reliability of density functional approximations.