The Nature of the Bonding in Transition-Metal Compounds

Frenking, Gernot; Fröhlich, Nikolaus

doi:10.1021/cr980401l

Cited by 1,173 publications

(969 citation statements)

References 349 publications

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“…Therefore, DFT is usually the method of choice in theoretical studies of transition-metal catalysis as well as molecular and spectroscopic properties of open-shell molecular systems. [22][23][24][25] Despite much success, it has also become clear that for openshell systems, DFT with the currently available approximate functionals shows a number of shortcomings. In addition to inaccuracies in predicting energies, geometries, and molecular properties (for a case study, see, e.g., Ref.…”

Section: Introductionmentioning

confidence: 99%

Spin in density‐functional theory

Jacob¹,

Reiher²

2012

Int J of Quantum Chemistry

225

224

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The accurate description of open-shell molecules, in particular of transition metal complexes and clusters, is still an important challenge for quantum chemistry. Although density-functional theory (DFT) is widely applied in this area, the sometimes severe limitations of its currently available approximate realizations often preclude its application as a predictive theory. Here, we review the foundations of DFT applied to open-shell systems, both within the nonrelativistic and the relativistic framework. In particular, we provide an in-depth discussion of the exact theory, with a focus on the role of the spin density and possibilities for targeting specific spin states. It turns out that different options exist for setting up Kohn-Sham DFT schemes for open-shell systems, which imply different definitions of the exchangecorrelation energy functional and lead to different exact conditions on this functional. Finally, we suggest possible directions for future developments.

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Section: Introductionmentioning

confidence: 99%

Spin in density‐functional theory

Jacob¹,

Reiher²

2012

Int J of Quantum Chemistry

225

224

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“…Difference density analysis as derived by highly resolved X-ray crystallography [1] and later modern quantum chemistry calculations (MO-theory -ab-initio, Morokuma [2], DFT [3] -or valence-bond theory, Pauling [4][5][6]) provide important insight into the nature of the metal-ligand bond. An extensive review on quantum chemical methods for analyzing the chemical bond and their applications to a wide range of closed shell TM complexes with organic ligands (carbene, carbyne, alkene, and alkyne -complexes) as well as complexes with CO, BF, BO À , BNH 2 , and H ligands has been published by Frenking and Fr€ o ohlich [7] and we refer the reader to their work.…”

Section: Introductionmentioning

confidence: 99%

Chemical Bonding in Molecules and Complexes Containing d-Elements Based on DFT

Atanasov

Daul

Fowe

2005

Monatshefte für Chemie

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Summary. Metal-ligand bonding in transition metal halide molecules and complexes with different central ions, oxidations states, and coordination numbers: Cr III X 6 3À , Cr IV X 4 , Cr II X 2 (X ¼ F,Cl,Br,I),3þ (M ¼ Cr,Co) and Re 2 Cl 8 2À has been studied in terms of the Extended Transition State (ETS) energy patitioning scheme within the DFT and electron density analysis (the Laplacian of the electron density and the electronic localization function). Bonding is found to be dominated by ionicity in all cases, especially so for complexes with higher coordination numbers. Covalent contributions to the metal-ligand bond are found to be mainly due to the ndelectrons and to lesser extent due to the metal (n þ 1)s and (n þ 1)p-orbitals, contributions from (n þ 1)s increasing when going to lower coordination numbers. Metal-ligand bonding analysis have been used in order to check some concepts emerging from ligand field theory when applied to the spectroscopy and magnetism of transition metal complexes. It is pointed out that for complexes of high symmetry (MX 6 , O h , MX 4 , T d , and MX 2 , D 1h ) electron density analyses gain interpretative power when partitioned into contributions from occupied orbitals of different symmetry.

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“…[24][25][26] During the last decade there has been much progress in quantum mechanical (QM) methods for high accuracy calculations on TM compounds and other heavy atom molecules. This has mostly become possible because of the application of the gradient-corrected DFT, ECP, MP2, CCSD, etc methods [23][24][25][26] which seem to give accurate geometries, energies and other important properties of TM molecules. Since bonding is expected most likely due to valence (atomic) molecular spinors, we shall discuss our calculated molecular spinor (orbital) energy levels of SgOC at the DF and NR levels of theory.…”

Section: Relativistic Electronic Structure Bonding and Molecularmentioning

confidence: 99%

Effects of relativity for atomization and isomerization energies of seaborgium carbonyl SgCO and seaborgium isocarbonyl SgOC: Relativity predicts SgOC to be more stable than SgCO

Malli

2015

AIP Advances

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Our ab initio all-electron fully relativistic Dirac-Fock (DF) and nonrelativistic Hartree-Fock (NR) calculations for seaborgium isocarbonyl SgOC predict atomization energy (AE) of 13.04 and 11.05 eV, respectively. However, the corresponding DF and NR atomization energies for the seaborgium carbonyl SgCO are predicted as 12.75 and 12.45 eV, respectively. This is the first such result in Chemistry where an isocarbonyl (and especially for a system of superheavy element Sg) is predicted to be more stable at the DF level of theory than the corresponding carbonyl. The predicted energy for the formation of the carbonyl SgCO at the relativistic DF and NR levels of theory is -54.90 and -50.95 kJ /mol, whereas the corresponding energy of formation of the isocarbonyl SgOC is -64.44 and -18.64 kJ/mol, respectively. Ours are the first results of relativistic effects for isomerization and atomization energies of the superheavy seaborgium isocarbonyl SgOC and its isomer SgCO.The formation of isocarbonyl SgOC, should be favored over the carbonyl isomer SgCO in the first step of the reaction Sg+CO → SgOC. C 2015 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License. [http://dx

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The Nature of the Bonding in Transition-Metal Compounds

Cited by 1,173 publications

References 349 publications

Spin in density‐functional theory

Spin in density‐functional theory

Chemical Bonding in Molecules and Complexes Containing d-Elements Based on DFT

Effects of relativity for atomization and isomerization energies of seaborgium carbonyl SgCO and seaborgium isocarbonyl SgOC: Relativity predicts SgOC to be more stable than SgCO

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