Journal ArticleDOI
Valence bond description of antiferromagnetic coupling in transition metal dimers
Reads0
Chats0
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
More filters
Journal ArticleDOI
Spectroscopic Evidence for Redox Isomerism in the 1,4-Diethynylbenzene-Bridged Heterobimetallic Cation [{Fe(dppe)Cp*}(μ-C≡CC6H4C≡C){Mo(dppe)(η-C7H7)}]PF6
Emma C. Fitzgerald,Emma C. Fitzgerald,Abdelkader Ladjarafi,Neil J. Brown,David Collison,Karine Costuas,Ruth Edge,Jean François Halet,Frédéric Justaud,Paul J. Low,Hacène Meghezzi,Thierry Roisnel,Mark W. Whiteley,Claude Lapinte +13 more
TL;DR: The reaction of [FeCl(dppe)Cp* with NaBPh4 in methanol gives the alkynylvinylidene complex [{Fe(dpp*)cp*}{μ-C≡CC6H4-4(H)C═C}{Mo(Dppe)(η-C7H7)}] BPh4, [2A]BPh 4, [2]Bph4,...
Journal ArticleDOI
Ligand-bound S = 1/2 FeMo-Cofactor of Nitrogenase: Hyperfine Interaction Analysis and Implication for the Central Ligand X Identity
TL;DR: Three different binding modes at single iron site and three different BS-DFT spin state structures are considered and it is shown that this binding would enhance the key hyperfine signal A(iso)(X) by at least 1 order of magnitude.
Journal ArticleDOI
Electrocatalytic oxygen evolution from water on a Mn(III–V) dimer model catalyst—A DFT perspective
TL;DR: The applicability of DFT is discussed and extended to include the rate-limiting steps in the OER, and an upper bound for the activation barrier of the O-O bond formation step is estimated from the hessians of the relevant intermediates.
Journal ArticleDOI
Applications of Density Functional Theory (DFT) to Investigate the Structural, Spectroscopic and Magnetic Properties of Lanthanide(III) Complexes
Carlos Platas-Iglesias,Adrián Roca-Sabio,Martín Regueiro-Figueroa,David Esteban-Gómez,Andrés de Blas,Teresa Rodríguez-Blas +5 more
TL;DR: In this article, the authors present an overview of different successful applications of density functional theory to investigate the structure, dynamics, vibrational spectra, NMR chemical shifts, hyperfine interactions, excited states, and magnetic properties of lanthanide(III) complexes.
Journal ArticleDOI
A family of [Mn6] complexes featuring tripodal ligands.
Constantinos J. Milios,Maria Manoli,Gopalan Rajaraman,Abhudaya Mishra,Laura Budd,Fraser J. White,Simon Parsons,Wolfgang Wernsdorfer,George Christou,Euan K. Brechin +9 more
TL;DR: The synthesis and magnetic properties of four new Mn complexes containing tripodal alcohol ligands and theoretical density functional calculations were used to evaluate the individual pairwise exchange interactions present, confirming the diamagnetic groundStates for 1 and 2 and the S = 4 ground states for 3 and 4.
References
More filters
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.