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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Catalysis of mononuclear aquaruthenium complexes in oxygen evolution from water: a new radical coupling path using hydroxocerium(IV) species.
TL;DR: Results indicate that the radical coupling between the oxygen atoms of a Ru(V)=O species and a hydroxocerium(IV) ion is the key step for the catalysis of [Ru(tmtacn)(R(2)bpy)(OH(2))](2+).
Journal ArticleDOI
Spin-restricted ensemble-referenced Kohn–Sham method: basic principles and application to strongly correlated ground and excited states of molecules
TL;DR: The spin-restricted ensemble-referenced Kohn-Sham (REKS) method represents perhaps the first computational scheme that makes ensemble density functional theory (DFT) calculations feasible.
Journal ArticleDOI
Analysing the chromium–chromium multiple bonds using multiconfigurational quantum chemistry
TL;DR: In this paper, the nature of the chemical bond between two chromium atoms in different di-chromium complexes with the metal atom in different oxidation states was discussed, based on multiconfigurational wave functions, which gave a qualitatively correct description of the electronic structure in these multiply bonded systems.
Journal ArticleDOI
Magnetic and spectroscopic properties of mixed valence manganese(III,IV) dimers: a systematic study using broken symmetry density functional theory.
TL;DR: It is demonstrated that the (55)Mn hyperfine couplings in mixed-valence Mn(III,IV) dimers can be successfully and systematically predicted with the TPSSh functional and the proposed spin projection techniques.
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.