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
Citations
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Metal−Metal Bonding in d1d1 and d2d2 Bioctahedral Dimer Systems: A Density Functional Study of Face-Shared M2X93- (M = Ti, Zr, Hf, V, Nb, Ta) Complexes
TL;DR: The global minimum for complete delocalization of the sigma and delta(pi) electrons occur in a metal-metal double bond, is found to be the global minimum and consequently relatively short internuclear distances result, in good agreement with experiment.
Journal ArticleDOI
Homoleptic Diphosphacyclobutadiene Complexes [M(η4-P2C2R2)2]x− (M=Fe, Co; x=0, 1)
Robert Wolf,Robert Wolf,Andreas W. Ehlers,Marat M. Khusniyarov,František Hartl,František Hartl,Bas de Bruin,Gary J. Long,Fernande Grandjean,Falko M. Schappacher,Rainer Pöttgen,J. Chris Slootweg,Martin Lutz,Anthony L. Spek,Koop Lammertsma +14 more
TL;DR: The preparation and comprehensive characterization of a series of homoleptic sandwich complexes containing diphosphacyclobutadiene ligands revealed the importance of covalent metal-ligand π bonding in 1-5.
Journal ArticleDOI
Mechanism and Enantioselectivity of Dirhodium-Catalyzed Intramolecular C–H Amination of Sulfamate
Xiting Zhang,Xiting Zhang,Zhuofeng Ke,Nathan J. DeYonker,Huiying Xu,Zhi-Feng Li,Xianyan Xu,Xuepeng Zhang,Cheng-Yong Su,David Lee Phillips,Cunyuan Zhao +10 more
TL;DR: The stepwise mechanism was found to hold also in the reaction of 3-phenylpropylsulfamate ester catalyzed by Rh2(S-nap)4, and the diradical intermediate also constitutes the starting point for competition steps involving enantioselectivity, which is determined by the C-N formation open-shell singlet transition state.
Journal ArticleDOI
Toward Tailored All-Spin Molecular Devices.
Maciej Bazarnik,Maciej Bazarnik,Bernhard Bugenhagen,Micha Elsebach,Emil Sierda,Annika Frank,Marc H. Prosenc,Roland Wiesendanger +7 more
TL;DR: It is shown that a more stable spintronic device could be achieved using tailored Co-Salophene based molecular building blocks, combined with in situ electrospray deposition under ultrahigh vacuum conditions as well as control of the surface-confined molecular assembly at the nanometer scale.
Journal ArticleDOI
Spin-flip time dependent density functional theory for singlet–triplet splittings in σ,σ-biradicals
Zilvinas Rinkevicius,Hans Ågren +1 more
TL;DR: A spin-flip time dependent density functional theory approach with hybrid non-collinear exchange correlation kernels has been applied to investigate the energy gap between the lowest singlet and triplet states of σ,σ-biradicals.
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.