Calculation of Ligand Dissociation Energies in Large Transition-Metal Complexes

Abstract: Despite the importance of ligand dissociation energies for computational chemistry, obtaining accurate ab initio reference data is difficult and density-functional methods of uncertain reliability are chosen for feasibility reasons. Here, we consider advanced coupled-cluster and multi-configurational approaches to reinvestigate our WCCR10 set of ten gas-phase ligand dissociation energies. We assess the potential multi-configurational character of all molecules involved in these reactions in order to determine where single-reference coupled-cluster approaches can be applied. For some reactions of the WCCR10 set, large deviations from density-functional results including semiclassical dispersion corrections from experimental reference data had been observed. We tackle the issue (i) by comparing to ab initio data that comprise dispersion effects on a rigorous first-principles footing and (ii) by a comparison of density-functional approaches that model dispersion interactions in various ways. Only for two reactions, species exhibiting nonnegligible static electron correlation were identified, and hence, we may choose standard single-reference coupled-cluster approaches to compare with density-functional methods for the other eight reactions. For WCCR10, the Minnesota M06-L functional yielded the smallest mean absolute deviation without additional dispersion corrections in comparison to the coupled-cluster results and the PBE0-D3 functional produced the overall smallest mean absolute deviation. The agreement of density-functional results with coupled-cluster data increases significantly upon inclusion of any type of dispersion correction. It is important to emphasize that different density-functional schemes available for this purpose perform equally well. The coupled-cluster dissociation energies, however, deviate significantly from experimental results.