Benchmark Study of the Performance of Density Functional Theory for Bond Activations with (Ni,Pd)-Based Transition-Metal Catalysts

Abstract

The performance of 23 density functionals, including one LDA, four GGAs, three meta-GGAs, three hybrid GGAs, eight hybrid meta-GGAs, and ten double-hybrid functionals, was investigated for the computation of activation energies of various covalent main-group single bonds by four catalysts: Pd, PdCl ⁻, PdCl ₂, and Ni (all in the singlet state). A reactant complex, the barrier, and reaction energy were considered, leading to 164 energy data points for statistical analysis. Extended Gaussian AO basis sets were used in all calculations. The best functional for the complete benchmark set relative to estimated CCSD(T)/CBS reference data is PBE0-D3, with an MAD value of 1.1 kcal mol ⁻¹ followed by PW6B95-D3, the double hybrid PWPB95-D3, and B3LYP-D3 (1.9 kcal mol ⁻¹ each). The other tested hybrid meta-GGAs perform less well (M06-HF: 7.0 kcal mol ⁻¹; M06-2X: 6.3 kcal mol ⁻¹; M06: 4.9 kcal mol ⁻¹) for the investigated reactions. In the Ni case, some double hybrids show larger errors due to partial breakdown of the perturbative treatment for the correlation energy in cases with difficult electronic structures (partial multi-reference character). Only double hybrids either with very low amounts of perturbative correlation (e.g., PBE0-DH) or that use the opposite-spin correlation component only (e.g., PWPB95) seem to be more robust. We also investigated the effect of the D3 dispersion correction. While the barriers are not affected by this correction, significant and mostly positive results were observed for reaction energies. Furthermore, six very recently proposed double-hybrid functionals were analyzed regarding the influence of the amount of Fock exchange as well as the type of perturbative correlation treatment. According to these results, double hybrids with <50–60 % of exact exchange and ∼30 % perturbative correlation perform best.