Journal ArticleDOI
Do f Electrons Play a Role in the Lanthanide-Ligand Bonds? A DFT Study of Ln(NR2)3; R = H, SiH3
TLDR
The participation of 4f electrons in the bonding of the lanthanide complexes Ln(NR2)3; R = H, SiH3, has been investigated at the DFT level as mentioned in this paper.Abstract:
The participation of 4f electrons in the bonding of the lanthanide complexes Ln(NR2)3; R = H, SiH3, has been investigated at the DFT level. Structural parameters obtained with small core (f electrons in the valence) and large core (f electrons in the core) effective core potentials (ECPs) suggest the nonparticipation of the f electrons to the Ln−N bonding. A methodological study has been carried out on the lanthanide contraction with various ab initio methods using large core ECPs. The calculated lanthanide contraction (0.180 A) is in excellent agreement with the experimental value (0.179 A). Comparison of calculated structural parameters with available X-ray data shows that calculations with large core ECPs and density functional methods quantitatively reproduce the bonding at the lanthanide.read more
Citations
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C-H bond activation in transition metal species from a computational perspective
TL;DR: The reactivity of pMMO has been explored by Chan,525 by means of DFT calculations on small models of Figure 116 and nonradical mechanism proposed in the Yoshizawa model of sMMO.
Journal ArticleDOI
Transition‐Metal Complexes Featuring Z‐Type Ligands: Agreement or Discrepancy between Geometry and dn Configuration?
Marie Sircoglou,Sébastien Bontemps,Maxime Mercy,Nathalie Saffon,Masashi Takahashi,Ghenwa Bouhadir,Laurent Maron,Didier Bourissou +7 more
Journal ArticleDOI
Lanthanide alkylidene and imido complexes.
TL;DR: A DFT (Density Functional Theory) study of a samarium imido complex has provided insight into the electronic and steric factors that may be necessary to support these unusual reactive groups.
Journal ArticleDOI
Covalency in lanthanides. An X-ray absorption spectroscopy and density functional theory study of LnCl6(x-) (x = 3, 2).
Matthias W. Löble,Jason M. Keith,Jason M. Keith,Alison B. Altman,S. Chantal E. Stieber,Enrique R. Batista,Kevin S. Boland,Steven D. Conradson,David Clark,Juan S. Lezama Pacheco,Stosh A. Kozimor,Richard L. Martin,Stefan G. Minasian,Angela C. Olson,Brian L. Scott,David K. Shuh,Tolek Tyliszczak,Marianne P. Wilkerson,Ralph A. Zehnder +18 more
TL;DR: Surprising 4f- and 5d-orbital participation in covalent bonding is presented in the context of recent studies on both tetravalent transition metal and actinide hexahalides, MCl6(2-) (M = Ti, Zr, Hf, U).
Journal ArticleDOI
Quantum chemistry-based interpretations on the lowest triplet state of luminescent lanthanides complexes. Part 1. Relation between the triplet state energy of hydroxamate complexes and their luminescence properties.
Fabien Gutierrez,Christine Tedeschi,Laurent Maron,Jean-Pierre Daudey,Romuald Poteau,Joëlle Azéma,Pierre Tisnès,Claude Picard +7 more
TL;DR: Results are an indication that this type of modelling can lead to discriminate in terms of the position of the lowest ligand triplet energy level the best antenna among a family of chromophoric compounds.
References
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Journal ArticleDOI
Density‐functional thermochemistry. III. The role of exact exchange
TL;DR: In this article, a semi-empirical exchange correlation functional with local spin density, gradient, and exact exchange terms was proposed. But this functional performed significantly better than previous functionals with gradient corrections only, and fits experimental atomization energies with an impressively small average absolute deviation of 2.4 kcal/mol.
Journal ArticleDOI
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
TL;DR: Numerical calculations on a number of atoms, positive ions, and molecules, of both open- and closed-shell type, show that density-functional formulas for the correlation energy and correlation potential give correlation energies within a few percent.
Journal ArticleDOI
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
TL;DR: The effective ionic radii of Shannon & Prewitt [Acta Cryst. (1969), B25, 925-945] are revised to include more unusual oxidation states and coordinations as mentioned in this paper.
Journal ArticleDOI
Note on an Approximation Treatment for Many-Electron Systems
Chr. Møller,Milton S. Plesset +1 more
TL;DR: In this article, a perturbation theory for treating a system of n electrons in which the Hartree-Fock solution appears as the zero-order approximation was developed, and it was shown by this development that the first order correction for the energy and the charge density of the system is zero.