Journal ArticleDOI
Valence bond description of antiferromagnetic coupling in transition metal dimers
TLDR
In this paper, a single configuration model containing nonorthogonal magnetic orbitals is developed to represent the important features of the antiferromagnetic state of a transition metal dimer.Abstract:
A single configuration model containing nonorthogonal magnetic orbitals is developed to represent the important features of the antiferromagnetic state of a transition metal dimer. A state of mixed spin symmetry and lowered space symmetry is constructed which has both conceptual and practical computational value. Either unrestricted Hartree–Fock theory or spin polarized density functional theory, e.g., Xα theory, can be used to generate the mixed spin state wave function. The most important consequence of the theory is that the Heisenberg exchange coupling constant J can be calculated simply from the energies of the mixed spin state and the highest pure spin multiplet.read more
Citations
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Journal ArticleDOI
O2 activation in a dinuclear Fe(II)/EDTA complex: spin surface crossing as a route to highly reactive Fe(IV)oxo species.
TL;DR: Using results from broken symmetry (BS) density functional theory (DFT) calculations, the cleavage of O2 in gas phase can be modeled as two high-spin S = 5/2 Fe(III) d5 centers coupled through a bridging peroxo O2(2-) ligand, consistent with hypotheses advanced in the literature.
Journal ArticleDOI
Exploring the interaction of N/S compounds with a dicopper center: tyrosinase inhibition and model studies.
Elina Buitrago,Alexandra Vuillamy,Ahcène Boumendjel,Wei Yi,Gisèle Gellon,Renaud Hardré,Christian Philouze,Guy Serratrice,Hélène Jamet,Marius Réglier,Catherine Belle +10 more
TL;DR: Investigation of phenylthiourea and phenylmethylene thiosemicarbazone recognized as inhibitors of tyrosinase by combining enzymatic studies and coordination chemistry methods confirms the high inhibitor efficiency of PTSC.
Journal ArticleDOI
DFT challenge of intermetallic interactions: From metallophilicity and metallaromaticity to sextuple bonding
TL;DR: The most recent advances in the chemistry of coordination compounds of the d - and f -block elements that contain d - d, f - f, or d - f metal-metal bonds are outlined in this paper.
Journal ArticleDOI
Vinylphosphirane-phospholene rearrangements: pericyclic [1,3]-sigmatropic shifts or not?
TL;DR: The conversion of "free" and Cr(CO)(5)-complexed 2-vinylphosphiranes into 3-phospholenes via [1,3]-sigmatropic shifts was studied with density functional theory and compared with the corresponding hydrocarbon system, that is, the vinylcyclopropane-cyclopentene rearrangement.
Journal ArticleDOI
Intra- and Interatomic Spin Interactions by the Density Functional Theory plus U Approach: A Critical Assessment
Yachao Zhang,Hong Jiang +1 more
TL;DR: This work finds that the DFT+U approach is an efficient and predictive first-principles method for the SCO phenomenon and interatomic magnetic interactions, and analyses the effect of U in terms of spin density on magnetic centers.
References
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Journal ArticleDOI
New Approach to the Theory of Superexchange Interactions
TL;DR: In this article, the theory of indirect exchange in poor conductors is examined from a new viewpoint in which the $d$ (or $f$) shell electrons are placed in wave functions assumed to be exact solutions of the problem of a single $d-electron in the presence of the full diamagnetic lattice.
Journal ArticleDOI
Orbital interactions in metal dimer complexes
TL;DR: In this paper, the effect of geometrical distortions, electronegativity, and variation of substituents on the magnetic interaction in dimeric systems is examined in detail for singly bridged L,M-X-ML, (n = 3, 4, 5); Cu~C16~ and other doubly bridging species where the bridging ligands are halogens, OR, pyridine N-oxides, oxalate, squarate; and the acetate bridged dimers C u ~ (R C 0 0 ) 4.
Journal ArticleDOI
Quantum Theory of Many-Particle Systems. III. Extension of the Hartree-Fock Scheme to Include Degenerate Systems and Correlation Effects
TL;DR: In this paper, it was shown that if the total wave function is approximated by a projection of a single determinant, the description of the system may be reduced to the ordinary Hartree-Fock scheme treating this determinant.
Book ChapterDOI
Scattered-Wave Theory of the Chemical Bond
TL;DR: In the self-consistent field (SCF)-Xα scattered-wave model that is also a first-principle technique, there is no basis set problem because Schrodinger's equation for an Xα potential is numerically integrated as discussed by the authors.