Geometry prediction of hafnocenes by quantum chemical methods

Karttunen, Virve A.; Linnolahti, Mikko; Pakkanen, Tapani A.; Maaranen, Janne; Pitkänen, Päivi

doi:10.1007/s00214-007-0375-6

Cited by 15 publications

(13 citation statements)

References 96 publications

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“…For Hf, Los Alamos ECP [15] (LANL2DZ) was employed and for Zr the Huzinaga's all-electron extra basis (Zr, 433 321/433/421) [16]. The applied combinations of methods and basis sets have been previously shown to provide reliable structures for hafnocenes [17] and zirconocenes [18]. Optimizations were carried out with the Gaussian03 program package [19].…”

Section: Methodsmentioning

confidence: 99%

The influence of the ligand structure on activation of hafnocene polymerization catalysts: A theoretical study

Karttunen

Linnolahti

Turunen

et al. 2008

Journal of Organometallic Chemistry

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Section: Methodsmentioning

confidence: 99%

The influence of the ligand structure on activation of hafnocene polymerization catalysts: A theoretical study

Karttunen

Linnolahti

Turunen

et al. 2008

Journal of Organometallic Chemistry

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“…Karttunen et al 407 tested B3LYP against WFT, in particular, Hartree-Fock theory and second-order perturbation theory (MP2) for geometry predictions on 80 hafnocenes in the Cambridge structural database. They found MP2 is most accurate, followed by Hartree-Fock theory, with B3LYP least accurate.…”

Section: Validation Studiesmentioning

confidence: 99%

Density functional theory for transition metals and transition metal chemistry

Cramer

Truhlar

2009

Phys. Chem. Chem. Phys.

1,487

1,342

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We introduce density functional theory and review recent progress in its application to transition metal chemistry. Topics covered include local, meta, hybrid, hybrid meta, and range-separated functionals, band theory, software, validation tests, and applications to spin states, magnetic exchange coupling, spectra, structure, reactivity, and catalysis, including molecules, clusters, nanoparticles, surfaces, and solids.

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“…This explains the continuous benchmarking of the electronic structure methods toward chemically more stressful situations, with publications indicating the limitation of a particular method or group of methods to accurately describe certain molecular properties or reaction energies. − Inspired by these documented failures and challenged by prohibitive costs of some electronic structure methods, efforts are constantly made to improve the methods’ performances and to reduce computational costs. This results in two big families of methods recommended for routine predictions in transition metal chemistry.…”

Section: Introductionmentioning

confidence: 99%

Troubles in the Systematic Prediction of Transition Metal Thermochemistry with Contemporary Out-of-the-Box Methods

Minenkov

Chermak

Cavallo

2016

J. Chem. Theory Comput.

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The recently developed DLPNO-CCSD(T) method and seven popular DFT functionals (B3LYP, M06, M06L, PBE, PBE0, TPSS, and TPSSh) with and without an empirical dispersion term have been tested to reproduce 111 gas phase reaction enthalpies involving 11 different transition metals. Our calculations, corrected for both relativistic effects and basis set incompleteness, indicate that most of the methods applied with default settings perform with acceptable accuracy on average. Nevertheless, our calculations also evidenced unexpected and nonsystematic large deviations for specific cases. For group 12 metals (Zn, Cd, Hg), most of the methods provided mean unsigned errors (MUE) less than 5.0 kcal/mol, with DLPNO-CCSD(T) and PBE methods performing excellently (MUE lower 2.0 kcal/mol). Problems started with group 4 metals (Ti and Zr). The best performer for Zr complexes with MUE of 1.8 kcal/mol, PBE0-D3, provides MUE larger than 8 kcal/mol for Ti. DLPNO-CCSD(T) provides a reasonable MUE of 3.3 kcal/mol for Ti reactions but gives MUE a larger than 14.4 kcal/mol for Zr complexes, with all the larger deviations for reactions involving ZrF4. Large and nonsystematic errors have been obtained for group 6 metals (Mo and W), for eight reactions containing Fe, Cu, Nb, and Re complexes. Finally, for the whole set of 111 reactions, the DLPNO-CCSD(T), B3LYP-D3, and PBE0-D3 methods turned out to be the best performers, all providing MUE below 5.0 kcal/mol. Since DFT results cannot be systematically improved and large nonsystematic deviations of 20-30 kcal/mol were obtained even for best performers, our results indicate that current DFT methods are still unable to provide robust predictions in transition metal thermochemistry, at least for the functionals explored in this work. The same conclusion holds for both DLPNO-CCSD(T) and canonical CCSD(T) methods when used entirely as out-of-the-box. However, if careful investigation of core correlation is performed, relativistic effects are properly included and the quality of the reference wave function is properly checked, CCSD(T) methods can still provide good quality results that might even be used to validate DFT methods due to paucity of accurate thermodynamic data for realistic-sized transition metal complexes.

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Geometry prediction of hafnocenes by quantum chemical methods

Cited by 15 publications

References 96 publications

The influence of the ligand structure on activation of hafnocene polymerization catalysts: A theoretical study

The influence of the ligand structure on activation of hafnocene polymerization catalysts: A theoretical study

Density functional theory for transition metals and transition metal chemistry

Troubles in the Systematic Prediction of Transition Metal Thermochemistry with Contemporary Out-of-the-Box Methods

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