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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Journal ArticleDOI
On the definition of local spin in relativistic and nonrelativistic quantum chemistry.
TL;DR: The transition from four-component theory to the two- and one-component Douglas-Kroll-Hess framework with respect to the electronic density is considered and the relevance of spin contamination and the effect of the approximate nature of contemporary density functionals is discussed.
Journal ArticleDOI
Electronic structures of tris(dioxolene)chromium and tris(dithiolene)chromium complexes of the electron-transfer series [Cr(dioxolene)(3)](z) and [Cr(dithiolene)(3)](z) (z = 0, 1-, 2-, 3-). A combined experimental and density functional theoretical study.
Ruta R. Kapre,Eberhard Bothe,Thomas Weyhermüller,Serena Debeer George,Nicoleta M. Muresan,Karl Wieghardt +5 more
TL;DR: Electrochemistry demonstrated that both species are members of the electron-transfer series [Cr(3,6LO,O] and all redox processes are ligand-based, corroborated by broken symmetry density functional theoretical calculations by using the B3LYP functional.
Journal ArticleDOI
A structural model for the high-valent intermediate Q of methane monooxygenase from broken-symmetry density functional and electrostatics calculations
TL;DR: A combined broken-symmetry density functional and electrostatics approach has been used to construct a model for the high-valent diiron intermediate Q of methane monooxygenase.
Journal ArticleDOI
Characterization of Redox States of Ru(OH2)(Q)(tpy)2+ (Q = 3,5-di-tert-butyl-1,2-benzoquinone, tpy = 2,2′:6′,2″-terpyridine) and Related Species through Experimental and Theoretical Studies
Ming Kang Tsai,Jonathan Rochford,Dmitry E. Polyansky,Tohru Wada,Koji Tanaka,Etsuko Fujita,James T. Muckerman +6 more
TL;DR: The redox states of Ru(OH(2))(Q)(tpy)(2+) (Q = 3,5-di-tert-butyl-1,2-benzoquinone, tpy = 2,2':6',2''-terpyridine) are investigated through experimental and theoretical UV-vis spectra and Pourbaix diagrams.
Journal ArticleDOI
Variable-Temperature, Variable-Field Magnetic Circular Dichroism Studies of Tris-Hydroxy- and μ3-Oxo-Bridged Trinuclear Cu(II) Complexes: Evaluation of Proposed Structures of the Native Intermediate of the Multicopper Oxidases
TL;DR: The Cu-O sigma-bonds in the mu3-oxo-bridged structure would provide the thermodynamic driving force for the 4e- reduction of O2 and would allow the facile electron transfer to all Cu centers in the trinuclear cluster that is consistent with its involvement in the catalytic cycle.
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.