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
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Journal ArticleDOI
Characterization of an amorphous iridium water-oxidation catalyst electrodeposited from organometallic precursors.
James D. Blakemore,Michael W. Mara,Michael W. Mara,Maxwell N. Kushner-Lenhoff,Nathan D. Schley,Steven J. Konezny,Ivan Rivalta,Ivan Rivalta,Christian F. A. Negre,Robert C. Snoeberger,Oleksandr Kokhan,Jier Huang,Andrew B. Stickrath,Lan Anh Tran,Maria L. Parr,Lin X. Chen,Lin X. Chen,David M. Tiede,Victor S. Batista,Robert H. Crabtree,Gary W. Brudvig +20 more
TL;DR: The steps leading to the formation of BL and its structure have been investigated by a combination of spectroscopic and theoretical methods, and it is shown that the carbon content of BL, while containing some C-H bonds intact at short times, is composed primarily of components with C═O fragments at longer times.
Journal ArticleDOI
Multiconfiguration Pair-Density Functional Theory: Barrier Heights and Main Group and Transition Metal Energetics
Rebecca K. Carlson,Giovanni Li Manni,Andrew L. Sonnenberger,Donald G. Truhlar,Laura Gagliardi +4 more
TL;DR: A broader test of the multiconfiguration pair-density functional theory is provided by applying it to bond energies of main-group molecules and transition metal complexes, barrier heights and reaction energies for diverse chemical reactions, proton affinities, and the water dimerization energy.
Journal ArticleDOI
Spectroscopic and Electronic Structure Studies of Intermediate X in Ribonucleotide Reductase R2 and Two Variants: A Description of the FeIV-Oxo Bond in the FeIII-O-FeIV Dimer
TL;DR: The assignment of the FeIV d-d transitions in WT intermediate X best correlates with a bridged mu-oxo/mu-hydroxo [FeIII(mu-O)(mu-OH)FeIV] structure, which provides an important sigma/pi superexchange pathway to promote facile electron transfer from Y122 to the remote FeIV through the bent oxo bridge, thereby generating the tyrosyl radical for catalysis.
Journal ArticleDOI
Theoretical studies of magnetic interactions in Mn(II)(hfac)(2)[di(4-pyridyl)phenylcarbene] and Cu(II)(hfac)(2)[di(4-pyridyl)phenylcarbene].
Yu Takano,Yasutaka Kitagawa,Taku Onishi,Yasunori Yoshioka,Kizashi Yamaguchi,Noboru Koga,Hiizu Iwamura +6 more
TL;DR: The spin alignment mechanisms of 1a and 2a are indeed consistent with SE plus SP rule, which is confirmed with the shape and symmetry of natural orbitals, together with charge and spin density distributions.
Journal ArticleDOI
Density Functional Study of the Photodissociation of Mn2(CO)10
TL;DR: In this article, potential energy curves have been calculated for a number of excited states of Mn2(CO)10, along the Mn−Mn bond dissociation coordinate and along Mn−COax and Mn− COeq coordinates, in order to understand why irradiation into the σ → σ* band does not only lead to Mn−mn bond breaking but also to Mn −CO dissociation.
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.