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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Theoretical analysis of spin crossover in iron(II) [2×2] molecular grids.
TL;DR: It is demonstrated that a succession of spin transitions on different centers depends on the character of the induced distortion, either approaching or getting them away from a more regular low-spin geometry, which can be modulated by weak perturbations such as a change of the positions of the hydrogen atoms.
Journal ArticleDOI
The open-cubane oxo-oxyl coupling mechanism dominates photosynthetic oxygen evolution: a comprehensive DFT investigation on O-O bond formation in the S4 state
TL;DR: DFT calculations corroborate the proposed water binding mechanism during S2-S3 transition and correlate the theoretical models with experimental findings from aspects of substrate selectivity according to water exchange kinetics, which may serve as a significant guide for improving the design and synthesis of biomimetic materials in the field of photocatalytic water splitting.
Journal ArticleDOI
Exploring the limits of redox non-innocence: pseudo square planar [{κ4-Me2C(CH2NCHpy)2}Ni]n (n = 2+, 1+, 0, −1, −2) favor Ni(II)
Valerie A. Williams,Elliott B. Hulley,Peter T. Wolczanski,Kyle M. Lancaster,Emil B. Lobkovsky +4 more
TL;DR: In this paper, the authors showed that Ni(COD)2 with Me2C(CH2NCHpy)2 (dmp(PI)2) afforded pseudo-square planar, diamagnetic NiII (Ni[0]), which contains radical anion pyridine-imine (PI) units bound to Ni(II).
Journal ArticleDOI
Protein environmental effects on iron-sulfur clusters: A set of rules for constructing computational models for inner and outer coordination spheres.
TL;DR: A set of general rules is proposed for constructing quantum chemical models for iron‐sulfur active sites that capture all significant interactions from the protein environment that capture the significance of a given protein environmental effect.
Journal ArticleDOI
Electronic structures and spectroscopy of the electron transfer series [Fe(NO)L2]z (z = 1+, 0, 1-, 2-, 3-; L = dithiolene).
Panida Surawatanawong,Stephen Sproules,Stephen Sproules,Frank Neese,Frank Neese,Karl Wieghardt +5 more
TL;DR: The calculated electronic structures give insight into how p-tolyl and CN substituents and the redox states of the 2 L ligand impact the spin density on the iron in the monocation and neutral species.
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.