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
Assessing Density Functional Theory for Chemically Relevant Open-Shell Transition Metal Reactions.
TL;DR: The ROST61 benchmark as mentioned in this paper is a single-reference open-shell (SOMC) benchmark set, which includes accurate coupled-cluster reference values for 61 reaction energies with a mean reaction energy of -42.8 kcal mol-1.
Journal ArticleDOI
Aromatic Hydroxylation in a Copper Bis(imine) Complex Mediated by a μ‐η2:η2 Peroxo Dicopper Core: A Mechanistic Scenario
Ole Sander,Anja Henß,Christian Näther,Christian Würtele,Max C. Holthausen,Siegfried Schindler,Felix Tuczek +6 more
TL;DR: Kinetic analysis of the ligand hydroxylation reaction shows that O2 binding is the rate-limiting step, and calculations predict the presence of a stable dienone intermediate which, however, escaped experimental detection so far.
Journal ArticleDOI
Ferrotoroidic Ground State in a Heterometallic Cr$^{\mathrm{III}}$Dy$^{\mathrm{III}}_6$ Complex Displaying Slow Magnetic Relaxation
Kuduva R. Vignesh,Alessandro Soncini,Stuart K. Langley,Wolfgang Wernsdorfer,Keith S. Murray,Gopalan Rajaraman +5 more
TL;DR: In this article, a Cr$^{\mathrm{III}$Dy$€{\mathm{III]µ€µµ-6$ complex with an enhanced toroidal moment, solely arising from intramolecular dipolar interactions, was isolated.
Journal ArticleDOI
XAS and DFT investigation of mononuclear cobalt(III) peroxo complexes: electronic control of the geometric structure in CoO2 versus NiO2 systems.
TL;DR: The results show that while the sterics of the cis-14-TMC chelate contribute to the geometry of O2 binding and result in an end-on-bound Ni(II)O2(-) complex in [(14- TMC)NiO2](+), the higher thermodynamic driving force for oxidation of Co(II), overcomes this steric constraint.
Journal ArticleDOI
Electronic structure of a weakly antiferromagnetically coupled Mn(II)Mn(III) model relevant to manganese proteins: a combined EPR, 55Mn-ENDOR, and DFT study.
Nicholas Cox,William Ames,William Ames,Boris Epel,Leonid V. Kulik,Leonid Rapatskiy,Frank Neese,Frank Neese,Johannes Messinger,Karl Wieghardt,Wolfgang Lubitz +10 more
TL;DR: This study demonstrates that DFT calculations provide reliable estimates for spectroscopic observables of mixed valence Mn complexes, even in the limit where the description of a well isolated S = 1/2 ground state begins to break down.
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.