Evaluation of density functional methods on the geometric and energetic descriptions of species involved in Cu+-promoted catalysis

Bernardo, Carlos E. P.; Bauman, Nicholas P.; Piecuch, Piotr; Silva, Pedro J.

doi:10.1007/s00894-013-2045-z

Cited by 8 publications

(5 citation statements)

References 58 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Notably, the overall MAD of HFS is even over 98 kJ/mol. Furthermore, we see that the much more expensive MP2 generally shows larger errors than most of the density functionals. − The large functional effect is not very surprising, and therefore, high-level methods are highly desirable if very accurate numbers are required …”

Section: Resultsmentioning

confidence: 91%

Benchmark Study on Methanol C–H and O–H Bond Activation by Bare [Fe^IVO]²⁺

Sun

Geng

et al. 2014

J. Phys. Chem. A

View full text Add to dashboard Cite

We present a high-level computational study on methanol C-H and O-H bond cleavages by bare [Fe(IV)O](2+), as well as benchmarks of various density functional theory (DFT) methods. We considered direct and concerted hydrogen transfer (DHT and CHT) pathways, respectively. The potential energy surfaces were constructed at the CCSD(T)/def2-TZVPP//B3LYP/def2-TZVP level of theory. Mechanistically, (1) the C-H bond cleavage is dominant and the O-H activation only plays minor role on the PESs; (2) the DHT from methyl should be the most practical channel; and (3) electronic structure analysis demonstrates the proton and electron transfer coupling behavior along the reaction coordinates. The solvent effect is evident and plays distinct roles in regulating the two bond activations in different mechanisms during the catalysis. The effect of optimizing the geometries using different density functionals was also studied, showing that it is not meaningful to discuss which DFT method could give the accurate prediction of the geometries, especially for transition structures. Furthermore, the gold-standard CCSD(T) method was used to benchmark 19 different density functionals with different Hartree-Fock exchange fractions. The results revealed that (i) the structural factor plays a minor role in the single point energy (SPE) calculations; (ii) reaction energy prediction is quite challenging for DFT methods; (iii) the mean absolute deviations (MADs) reflect the problematic description of the DFs when dealing with metal oxidation state change, giving a strong correlation on the HF exchange in the DFs. Knowledge from this study should be of great value for computational chemistry, especially for the de novo design of transition metal catalysts.

show abstract

Section: Resultsmentioning

confidence: 91%

Benchmark Study on Methanol C–H and O–H Bond Activation by Bare [Fe^IVO]²⁺

Sun

Geng

et al. 2014

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…Because DFT is in fact a family of methods (in other words, density functionals), and each of them presents an approximate approach to the unknown exact density functional, the approximations used in a given DFT method affect its accuracy in modeling a specific molecular system. Therefore, each density functional requires testing prior to its application and many studies evaluating the performance of density functionals for various organometallic systems and inorganic systems containing metal atoms have been published, e.g., [ 6 – 10 ] to mention only a few of the most recent.…”

Section: Introductionmentioning

confidence: 99%

Performance of Møller-Plesset second-order perturbation theory and density functional theory in predicting the interaction between stannylenes and aromatic molecules

Matczak

Wojtulewski

2015

J Mol Model

View full text Add to dashboard Cite

The performances of Møller-Plesset second-order perturbation theory (MP2) and density functional theory (DFT) have been assessed for the purposes of investigating the interaction between stannylenes and aromatic molecules. The complexes between SnX2 (where X = H, F, Cl, Br, and I) and benzene or pyridine are considered. Structural and energetic properties of such complexes are calculated using six MP2-type and 14 DFT methods. The assessment of the above-mentioned methods is based on the comparison of the structures and interaction energies predicted by these methods with reference computational data. A very detailed analysis of the performances of the MP2-type and DFT methods is carried out for two complexes, namely SnH2-benzene and SnH2-pyridine. Of the MP2-type methods, the reference structure of SnH2-benzene is reproduced best by SOS-MP2, whereas SCS-MP2 is capable of mimicking the reference structure of SnH2-pyridine with the greatest accuracy. The latter method performs best in predicting the interaction energy between SnH2 and benzene or pyridine. Among the DFT methods, ωB97X provides the structures and interaction energies of the SnH2-benzene and SnH2-pyridine complexes with good accuracy. However, this density functional is not as effective in reproducing the reference data for the two complexes as the best performing MP2-type methods. Next, the DFT methods are evaluated using the full test set of SnX2-benzene and SnX2-pyridine complexes. It is found that the range-separated hybrid or dispersion-corrected density functionals should be used for describing the interaction in such complexes with reasonable accuracy.Electronic supplementary materialThe online version of this article (doi:10.1007/s00894-015-2589-1) contains supplementary material, which is available to authorized users.

show abstract

“…Earlier work has shown that the PBE family of functionals (specifically PBE0 and PBE1PW91) usually affords the best agreement with MP2 and CCSD(T) computations on the energetic and geometric characterization of Cu + -iodoalkyne complexes. 62 An additional benchmarking study for the singlestep addition of azide to 1-iodopropyne (Table 1 and Supporting Information) confirmed the suitability of the PBE family of functionals and showed that PBEPW91, which agreed within 1 kcal•mol −1 with the MP2 activation energy, would be the best choice for a thorough DFT-based exploration of the potential energy surface of this reaction. The inclusion of dispersion effects through Grimme's D3 formalism improved the performance of most functionals but did not afford a better agreement of PBEPW91 with the reference MP2 computations.…”

Section: ■ Resultsmentioning

confidence: 76%

Influence of Alkyne and Azide Substituents on the Choice of the Reaction Mechanism of the Cu⁺-Catalyzed Addition of Azides to Iodoalkynes

Silva

Bernardo

2018

J. Phys. Chem. A

Self Cite

View full text Add to dashboard Cite

The cycloaddition of azides to iodoalkynes is strongly enhanced by some Cu-complexes. We have studied computationally six reaction pathways for the cycloaddition of 24 combinations of azide and iodoalkyne to identify the dominant pathways and the influence of reactant structure on the evolution of the reaction. Two pathways were found to be operating for distinct sets of reactants. In the first pathway, initial complexation of iodoalkyne by Cu is followed by the binding of the azide to the metal through its substituted nitrogen atom, followed by attack of the nonhalogenated alkyne carbon by the terminal nitrogen atom. This pathway is generally followed by aromatic or electron-deficient azides, unless the iodoalkyne bears an electron-withdrawing group. The second pathway is a single-step mechanism similar (apart from the alkyne bond weakening caused by complexation) to that observed in the absence of catalyst. Electron-deficient iodoalkynes and methyl azides strongly prefer this mechanism, regardless of the identity of the reaction partners. The catalytic gain obtained through the use of Cu depends only partially on its direct effect on the energy of the transition state (relative to that of the infinitely separated reactants) and may be lost if the iodoalkyne itself strongly interacts with the catalyst through the formation of too strong a π-complex.

show abstract

Evaluation of density functional methods on the geometric and energetic descriptions of species involved in Cu+-promoted catalysis

Cited by 8 publications

References 58 publications

Benchmark Study on Methanol C–H and O–H Bond Activation by Bare [Fe^IVO]²⁺

Benchmark Study on Methanol C–H and O–H Bond Activation by Bare [Fe^IVO]²⁺

Performance of Møller-Plesset second-order perturbation theory and density functional theory in predicting the interaction between stannylenes and aromatic molecules

Influence of Alkyne and Azide Substituents on the Choice of the Reaction Mechanism of the Cu⁺-Catalyzed Addition of Azides to Iodoalkynes

Contact Info

Product

Resources

About

Evaluation of density functional methods on the geometric and energetic descriptions of species involved in Cu+-promoted catalysis

Cited by 8 publications

References 58 publications

Benchmark Study on Methanol C–H and O–H Bond Activation by Bare [FeIVO]2+

Benchmark Study on Methanol C–H and O–H Bond Activation by Bare [FeIVO]2+

Performance of Møller-Plesset second-order perturbation theory and density functional theory in predicting the interaction between stannylenes and aromatic molecules

Influence of Alkyne and Azide Substituents on the Choice of the Reaction Mechanism of the Cu+-Catalyzed Addition of Azides to Iodoalkynes

Contact Info

Product

Resources

About

Benchmark Study on Methanol C–H and O–H Bond Activation by Bare [Fe^IVO]²⁺

Benchmark Study on Methanol C–H and O–H Bond Activation by Bare [Fe^IVO]²⁺

Influence of Alkyne and Azide Substituents on the Choice of the Reaction Mechanism of the Cu⁺-Catalyzed Addition of Azides to Iodoalkynes