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(-), PdCl2, 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 hybr

SUBMITTER: Steinmetz M 

PROVIDER: S-EPMC3703816 | biostudies-literature | 2013 Jun

REPOSITORIES: biostudies-literature