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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Journal ArticleDOI
Spin-State Energetics of Fe Complexes from an Optimally Tuned Range-Separated Hybrid Functional
Georgia Prokopiou,Leeor Kronik +1 more
TL;DR: In this paper, the performance of the optimally tuned range-separated hybrid (OT-RSH) functional approach was assessed in predicting the ground-state electronic configuration and spin-state energetics of complexes that can potentially exhibit multiple spin configurations.
Journal ArticleDOI
S K-edge X-ray absorption spectroscopy and density functional theory studies of high and low spin {FeNO}7 thiolate complexes: exchange stabilization of electron delocalization in {FeNO}7 and {FeO2}8.
Ning Sun,Lei V. Liu,Abhishek Dey,Gloria Villar-Acevedo,Julie A. Kovacs,Marcetta Y. Darensbourg,Keith O. Hodgson,Britt Hedman,Edward I. Solomon +8 more
TL;DR: These studies demonstrate how the ligand field of the Fe center defines its spin state and thus changes the electron exchange, an important factor in determining the electron distribution over {FeNO}(7) and {FeO2}(8) sites.
Journal ArticleDOI
Radical Chemistry of Iminepyridine Ligands
TL;DR: In this paper, the reactivity of metal fragments MeLi(THF), Me2Mg, Me2Zn and Me3Al with a variety of imine/pyridine ligands was studied by DFT methods.
Journal ArticleDOI
Density Functional Theory Prediction of Enhanced Photomagnetic Properties of Nitronyl Nitroxide and Imino Nitroxide Diradicals with Substituded Dihydropyrene Couplers
Md. Ehesan Ali,Sambhu N. Datta +1 more
TL;DR: It is predicted that the photoswitching magnetic properties of four substituted dihydropyrenes from density functional broken-symmetry calculations will be similar to those reported earlier for photomagnetic organic molecules.
Journal ArticleDOI
Electronic Structures of Five‐Coordinate Complexes of Iron Containing Zero, One, or Two π‐Radical Ligands: A Broken‐Symmetry Density Functional Theoretical Study
TL;DR: It is shown unambiguously for the first time that the pentane-2,4-dione-bis(S-alkylisothiosemicarbazonato) ligand can bind as pi-radical dianion (L.TSC)2- in [FeIII(CN)2(L. TSC)I] (St=1) (6); the description as [Fe IV(L TSC(3-))I] is incorrect.
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.