Journal ArticleDOI
Valence bond description of antiferromagnetic coupling in transition metal dimers
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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
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Bis(α-diimine)iron complexes: Electronic structure determination by spectroscopy and broken symmetry density functional theoretical calculations
Nicoleta M. Muresan,Connie C. Lu,Meenakshi Ghosh,Jonas C. Peters,Megumi Abe,Lawrence M. Henling,Thomas Weyhermöller,Eckhard Bill,Karl Wieghardt +8 more
TL;DR: The study confirms that alpha-diimines are redox noninnocent ligands with an energetically low-lying antibonding pi* lowest unoccupied molecular orbital which can accept one or two electrons from a transition metal ion.
Journal ArticleDOI
Mechanism of Pd(OAc)2/Pyridine Catalyst Reoxidation by O2: Influence of Labile Monodentate Ligands and Identification of a Biomimetic Mechanism for O2 Activation
Brian V. Popp,Shannon S. Stahl +1 more
TL;DR: Investigations of the mechanism of the reaction of O(2) with the Pd(0) intermediate revealed a novel, previously unrecognized mechanism that yields a Pd-OOH product without proceeding through the intermediacy of a PD(II)(eta(2)-peroxo) species.
Journal ArticleDOI
Borylated Dibenzoborepin: Synthesis by Skeletal Rearrangement and Photochromism Based on Bora-Nazarov Cyclization
Journal ArticleDOI
Quantum chemical interpretation of redox properties of ruthenium complexes with vinyl and TCNX type non-innocent ligands
TL;DR: An overview of density functional theory (DFT) calculations with spectroelectrochemical measurements on mononuclear and symmetrically or unsymmetrically bridged di-and tetranuclear ruthenium complexes of vinyl and TCNX ligands is given in this paper.
Journal ArticleDOI
Role of the Metal in the Bonding and Properties of Bimetallic Complexes Involving Manganese, Iron, and Cobalt
Stephen J. Tereniak,Rebecca K. Carlson,Laura J. Clouston,Victor G. Young,Eckhard Bill,Rémi Maurice,Yu-Sheng Chen,Hyun Jung Kim,Laura Gagliardi,Connie C. Lu +9 more
TL;DR: It is proposed that the diiron system has delocalized metal-metal bonding electrons, which seems to correlate with a short metal- metal bond and a higher spin state.
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.