Journal ArticleDOI
Valence bond description of antiferromagnetic coupling in transition metal dimers
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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
Reversible Visible-Light Photooxidation of an Oxomanganese Water-Oxidation Catalyst Covalently Anchored to TiO2 Nanoparticles†
Gonghu Li,Eduardo M. Sproviero,William R. McNamara,Robert C. Snoeberger,Robert H. Crabtree,Gary W. Brudvig,Victor S. Batista +6 more
TL;DR: The covalent attachment of 1 onto nanoparticulate TiO(2) surfaces using a robust chromophoric linker L, a phenylterpy ligand attached to a 3-phenyl-acetylacetonate anchoring moiety via an amide bond, absorbs visible light and leads to photoinduced interfacial electron transfer into the TiO (2) conduction band.
Journal ArticleDOI
Quantum chemical characterization of the mechanism of a supported cobalt-based water oxidation catalyst
TL;DR: F Fluorination of the supporting corrole appears both to modulate the electrophilicity of the metal-oxo fragment and to mitigate decomposition reactions that might otherwise be expected for a corrole radical cation.
Book ChapterDOI
Electronic Structure and Magnetic Behavior in Polynuclear Transition‐Metal Compounds
Eliseo Ruiz,Santiago Alvarez,Antonio Rodríguez-Fortea,Pere Alemany,Yann Pouillon,Carlo Massobrio +5 more
Journal ArticleDOI
Probing the Balance between Localization and Delocalization of the Metal-Based Electrons in Face-Shared Bioctahedral Complexes.
TL;DR: The overall trend is toward greater localization of the metal-based electrons in complexes of the manganese triad, where metal-metal interactions range from strong multiple bonding to weak antiferromagnetic coupling.
Journal ArticleDOI
Spin states in polynuclear clusters: The [Fe2O2] core of the methane monooxygenase active site
TL;DR: It is found that exact exchange enhances local spin polarization as the exact exchange admixture increases, and the high‐spin state is energetically favored, although the Broken‐Symmetry state always is the ground 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.