Validation of Hybrid Density Functional/Hartree−Fock Approaches for the Study of Homogeneous Catalysis

Abstract

The potentialities of a hybrid density functional/Hartree-Fock approach in the study of homogeneous catalysis have been investigated by a comprehensive study of binary adducts of copper atom characterized by strong (Cu 2 , CuH, CuCH 3 ) or weak (CuCO, CuNO, CuO 2 , CuC 2 H 2 ) metal-ligand interactions. The results confirm that this approach describes with good accuracy several properties of transition metal complexes, giving in particular binding energies close to the best available post-Hartree-Fock and experimental results. Besides the reasonable computation times, the possibility of avoiding high angular momentum basis functions, and the negligible basis set superposition error, the strength of hybrid approaches is their remarkably constant accuracy for closed-and open-shell systems and for strong covalent or weak donor-acceptor interactions. Furthermore, the ease of interpretation of single-determinant methods is retained. This allows the use of powerful energy decomposition tools for gaining further insight into the origin of different bonding patterns.

Molecular structures and vibrations of neutral and anionicCuOx(x=1–3,6Baruah1, Zope2, Pederson3 2004Phys. Rev. A20290View full textAdd to dashboardCite

“…However, the order of isomers as the structures A, C, and B in increasing energy observed in earlier DFT works is now altered in the present work due to the new isomer (D) found in this work. This isomer is the next low-lying isomer to the lowest energy [14,21,23]. The lowest-energy structure has a doublet state in agreement with the experimental observation [12,16].…”

“…Our vibrational frequency calculations have shown that the side on C isomer has one imaginary frequency. Such imaginary frequency for this isomer has also been observed in the earlier density functional based work of Barone and Adamo [14]. Earlier quantum chemical calculation by Bauschlicher [23] found isomer C to be more stable than the bent structure A.…”

The Chatt-Dewar-Duncanson Model Revisited: X-ray, DFT and NMR Studies of Rhodium-Alkene Binding—Deviations from Structural Ideality

“…DFT calculations are discussed first. The Kohn ± Sham formulation of density functional theory provides geometric data for transition metal complexes (amongst others) that are comparable with highly correlated Hartree ± Fock calculations [19] and leads to molecular orbitals with a good physical basis; [20] thus we have confidence in using these in our analyses.…”

Effects of oxygenates and moisture on adsorptive desulfurization of liquid fuels with Cu(I)Y zeolite

“…A hybrid method consisting of HF and DFT, known as the self-consistent hybrid (SCH) approach or B3LYP [16,17] approach is used. The B3LYP method can provide reliable geometric, thermodynamic and spectroscopic parameters for metal-ligand interactions, ranging from covalent bonds to weak non-covalent interactions [18][19][20]. It is the combination of HF and Becke exchange [21] with the Lee-Yang-Parr (LYP) correlation potential [22].…”