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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 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.

SUBMITTER: Steinmetz M

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

REPOSITORIES: biostudies-other

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Benchmark study of the performance of density functional theory for bond activations with (ni,pd)-based transition-metal catalysts.

Steinmetz Marc M Grimme Stefan S

ChemistryOpen 20130603 3

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 bas ...[more]

PMID: 24551548

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Project description:Multicenter transition-metal complexes (MCTMs) with magnetically interacting ions have been proposed as components for information-processing devices and storage units. For any practical application of MCTMs as magnetic units, it is crucial to characterize their magnetic behavior, and in particular, the isotropic magnetic exchange coupling, J, between its magnetic centers. Due to the large size of typical MCTMs, density functional theory is the only practical electronic structure method for evaluating the J coupling. Here, we assess the accuracy of different density functional approximations for predicting the magnetic couplings of eight dinuclear transition-metal complexes, including five dimanganese, two dicopper, and one divanadium with known reliable experimental J couplings spanning from ferromagnetic to strong antiferromagnetic. The density functionals considered include global hybrid functionals which mix semilocal density functional approximations and exact exchange with a fixed admixing parameter, six local hybrid functionals where the admixing parameters are extended to be spatially dependent, the SCAN and r2SCAN meta-generalized gradient approximations (GGAs), and two widely used GGAs. We found that global hybrids tested in this work have a tendency to over-correct the error in magnetic coupling parameters from the Perdew-Burke-Ernzerhof (PBE) GGA as seen for manganese complexes. The performance of local hybrid density functionals shows no improvement in terms of bias and is scattered without a clear trend, suggesting that more efforts are needed for the extension from global to local hybrid density functionals for this particular property. The SCAN and r2SCAN meta-GGAs are found to perform as well as benchmark global hybrids on most tested complexes. We further analyze the charge density redistribution of meta-GGAs as well as global and local hybrid density functionals with respect to that of PBE, in connection to the self-interaction error or delocalization error.

Dataset Information

Benchmark study of the performance of density functional theory for bond activations with (ni,pd)-based transition-metal catalysts.

Publications

Benchmark study of the performance of density functional theory for bond activations with (ni,pd)-based transition-metal catalysts.

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