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
Electronic structure of the [tris(dithiolene)chromium](z) (z = 0, 1-, 2-, 3-) electron transfer series and their manganese(IV) analogues. An X-ray absorption spectroscopic and density functional theoretical study.
Priyabrata Banerjee,Stephen Sproules,Thomas Weyhermüller,Serena DeBeer George,Karl Wieghardt +4 more
TL;DR: It is shown by chromium K-edge and sulfur K- edge X-ray absorption spectroscopy (XAS) that the oxidation state of the central Cr ion in each compound is the same (+III, d(3)) and that all one-electron redox processes are ligand-based, involving one, two, or three ligand pi radical monoanions.
Journal ArticleDOI
Breathing Some New Life into an Old Topic: Chalcogen-Nitrogen π-Heterocycles as Electron Acceptors
TL;DR: Recent progress in the design, synthesis and characterization of chalcogen-nitrogen π-heterocycles, mostly 1,2,5-chalcogenadiazoles (chalCogen: S, Se and Te) and their fused derivatives, possessing positive electron affinity is discussed together with their use in preparation of charge-transfer complexes and radical-anion salts.
Journal ArticleDOI
Cr2 in density-functional theory: approximate spin projection
TL;DR: In this paper, the ground state potential energy curve of Cr 2 is examined using three density-functional exchange-correlation approximations: the local spin-density approximation (LSDA), the gradient-corrected BLYP approximation, and the recent B3P86 approximation incorporating a small admixture of exact exchange.
Journal ArticleDOI
A Step beyond the Feltham–Enemark Notation: Spectroscopic and Correlated ab Initio Computational Support for an Antiferromagnetically Coupled M(II)–(NO)− Description of Tp*M(NO) (M = Co, Ni)
Neil C. Tomson,Mark R. Crimmin,Taras Petrenko,Lauren E. Rosebrugh,Stephen Sproules,W. Christopher Boyd,Robert G. Bergman,Serena DeBeer,F. Dean Toste,Karl Wieghardt +9 more
TL;DR: Computational studies in conjunction with quasi-degenerate perturbation theory with respect to spin-orbit coupling were required for obtaining accurate modeling of the molecular g-tensor, and a comparison of the DFT and ab initio computational methods for their ability to predict various spectroscopic and molecular features is discussed.
Journal ArticleDOI
The two oxidized forms of the trinuclear Cu cluster in the multicopper oxidases and mechanism for the decay of the native intermediate
Jungjoo Yoon,Barry D. Liboiron,Ritimukta Sarangi,Keith O. Hodgson,Britt Hedman,Edward I. Solomon +5 more
TL;DR: Comparison of the spectral features of NI and NIAz, combined with density functional theory (DFT) calculations, allows refinement of the NI structure, which is consistent with the slow rate of NI decay that uncouples the resting enzyme from 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.