Journal ArticleDOI
Valence bond description of antiferromagnetic coupling in transition metal dimers
Reads0
Chats0
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
More filters
Journal ArticleDOI
The catalytic activities and magnetic behaviours of rare μ3-chlorido and μ1,1,1-azido bridged defective dicubane tetranuclear Mn(ii) complexes.
TL;DR: Variable temperature magnetic susceptibility measurements of a solid sample reveal that both the complexes are antiferromagnetically coupled.
Journal ArticleDOI
Probing the Magnetic Anisotropy of Co(II) Complexes Featuring Redox-Active Ligands.
Praveen Kumar,Daniel J. SantaLucia,Kinga Kaniewska-Laskowska,Sergey V. Lindeman,Andrew Ozarowski,J. Krzystek,Mykhaylo Ozerov,Joshua Telser,John F. Berry,Adam T. Fiedler +9 more
TL;DR: Multireference ab initio calculations, using the CASSCF/NEVPT2 approach, indicate that the strongly negative anisotropies of these Co(II) complexes arise primarily from distortions in the equatorial plane due to constrictions imposed by the TpPh2 ligand.
Journal ArticleDOI
A disilapentalene and a stable diradical from the reaction of a dilithiosilole with a dichlorocyclopropene.
TL;DR: In this paper, the trans-trans isomer of diradical 3 was calculated to be more stable than its cis-cis isomer, and a reaction scheme describing the formation of 3 and 4 was presented.
Journal ArticleDOI
Computational study of iron bis(dithiolene) complexes: redox non-innocent ligands and antiferromagnetic coupling.
Heiko Jacobsen,James P. Donahue +1 more
TL;DR: A model for reversible, electrochemically controlled binding and release of phosphine ligands to iron bis(dithiolene) complexes is proposed and BP86 calculations provide the best quantitative match in comparison with the experiment.
Journal ArticleDOI
Elucidating the 2D magnetic topology of the 'metal-radical' TTTA⋅Cu(hfac)2 system.
TL;DR: In the metal-radical TTTA⋅Cu(hfac)2 compound, the computational model transcends the local dimer cluster model owing to strong interactions between metal centers and organic radicals, thereby creating a de facto biradical.
References
More filters
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.