New Benchmark Set of Transition-Metal Coordination Reactions for the Assessment of Density Functionals.

Abstract

We present the WCCR10 data set of 10 ligand dissociation energies of large cationic transition metal complexes for the assessment of approximate exchange-correlation functionals. We analyze nine popular functionals, namely BP86, BP86-D3, B3LYP, B3LYP-D3, B97-D-D2, PBE, TPSS, PBE0, and TPSSh by mutual comparison and by comparison to experimental gas-phase data measured with well-known precision. The comparison of all calculated data reveals a large, system-dependent scattering of results with nonnegligible consequences for computational chemistry studies on transition metal compounds. Considering further the comparison with experimental results, the nonempirical functionals PBE and TPSS turn out to be among the best functionals for our reference data set. The deviation can be lowered further by including Hartree-Fock exchange. Accordingly, PBE0 and TPSSh are the two most accurate functionals for our test set, but also these functionals exhibit deviations from experimental results by up to 50 kJ mol(-1) for individual reactions. As an important result, we found no functional to be reliable for all reactions. Furthermore, for some of the ligand dissociation energies studied in this work, invoking semiempirical dispersion corrections yields results which increase the deviation from experimental results. This deviation increases further if structure optimization including such dispersion corrections is performed, although the contrary should be the case, pointing to the need to develop the currently available dispersion corrections further. Finally, we compare our results to other benchmark studies and highlight that the performance assessed for different density functionals depends significantly on the reference molecule set chosen.