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
Mononuclear, Dinuclear, and Pentanuclear [{N,S(thiolate)}Iron(II)] Complexes: Nuclearity Control, Incorporation of Hydroxide Bridging Ligands, and Magnetic Behavior
Divya Krishnamurthy,Amy Narducci Sarjeant,David P. Goldberg,Andrea Caneschi,Federico Totti,Lev N. Zakharov,Arnold L. Rheingold +6 more
TL;DR: To provide entry into hydroxide-containing complexes, a novel synthetic method was developed involving strict aprotic conditions and limiting amounts of H2O, which led to the isolation of the pentanuclear, mu-OH complex 3, which has a novel dimer-of-dimers type structure connected by a central iron atom.
Journal ArticleDOI
Toward an effective yet reliable many-body computation of magnetic couplings in bisnitronyl nitroxide biradicals.
TL;DR: Configuration interaction calculations have been applied to the study of the magnetic coupling in a series of bisnitronyl nitroxide diradicals, with the aim of investigating the role played by the various fragments in the magnetic interaction.
Journal ArticleDOI
ENDOR Characterization of a Synthetic Diiron Hydrazido Complex as a Model for Nitrogenase Intermediates
Nicholas S. Lees,Rebecca L. McNaughton,Wilda Vargas Gregory,Patrick L. Holland,Brian M. Hoffman +4 more
TL;DR: The results support the use of DFT computations in identifying nitrogenous species bound to FeMo-co of nitrogenase turnover intermediates and indicate that 14N quadrupole parameters from nitrogenase intermediates will provide a strong indication of the nature of the bound nitrogenousspecies.
Journal ArticleDOI
Redox potential of the Rieske iron-sulfur protein quantum-chemical and electrostatic study.
TL;DR: Quantum-chemical study of structures, energies, and effective partial charge distribution for several models of the Rieske protein redox center is performed in terms of the B3LYP density functional method in combination with the broken symmetry approach using three different atomic basis sets for reasonable agreement of the calculated and experimental redox potentials.
Journal ArticleDOI
A T‐Shaped μ3‐Oxido Trinuclear Iron Cluster with High Easy‐Plane Anisotropy: Structural and Magnetic Characterization
Pablo Alborés,Eva Rentschler +1 more
TL;DR: In this article, the synthesis, crystal structure and magnetochemical characterization of a new μ-oxido trinuclear iron cluster [Fe3(μ3-O)(μ2-CH3O)2(μ2 -CH3COO)2 (phen)2Cl3], is reported.
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.