Search results for "Superexchange"
showing 10 items of 25 documents
Crystal structure and mössbauer spectroscopy studies of the ferrimagnetic complex bimetallic salt hexaamminechromium (III) hexachloroferrate (III), […
1992
The crystal and molecular structures of the ferrimagnetic bimetallic complex salt hexaamminechromium(III) hexachloroferrate(III), [Cr(NH3)6][FeCl6], have been determined from single-crystal, three-dimensional x-ray diffraction counter data. The compound crystallizes as orange coloured crystals in the space groupC2/c of the monoclinic system with Z=4 and has cell dimensionsa=11.325(1) A,b=11.387(1) A,c=11.233(1) A, and β=90.83(1)A. The structure was refined by using segmented block diagonal least-squares techniques to discrepancy indices R and Rw of 0.0233 and 0.0285, respectively. The metal ions occupy sites with symmetry $$\bar 1$$ and are nearly octahedrally coordinated. In the [FeCl6]3− …
Defect-Induced Orbital Polarization and Collapse of Orbital Order in Doped Vanadium Perovskites
2018
We explore mechanisms of orbital order decay in doped Mott insulators $R_{1-x}$(Sr,Ca)$_x$VO$_3$ ($R=\,$Pr,Y,La) caused by charged (Sr,Ca) defects. Our unrestricted Hartree-Fock analysis focuses on the combined effect of random, charged impurities and associated doped holes up to $x=0.5$. The study is based on a generalized multi-band Hubbard model for the relevant vanadium $t_{2g}$ electrons, and includes the long-range (i) Coulomb potentials of defects and (ii) electron-electron interactions. We show that the rotation of occupied $t_{2g}$ orbitals, induced by the electric field of defects, is a very efficient perturbation that largely controls the suppression of orbital order in these com…
Time-resolved Observation and Control of Superexchange Interactions with Ultracold Atoms in Optical Lattices
2007
Quantum mechanical superexchange interactions form the basis of quantum magnetism in strongly correlated electronic media. We report on the direct measurement of superexchange interactions with ultracold atoms in optical lattices. After preparing a spin-mixture of ultracold atoms in an antiferromagnetically ordered state, we measure a coherent superexchange-mediated spin dynamics with coupling energies from 5 Hz up to 1 kHz. By dynamically modifying the potential bias between neighboring lattice sites, the magnitude and sign of the superexchange interaction can be controlled, thus allowing the system to be switched between antiferromagnetic or ferromagnetic spin interactions. We compare our…
A new tetranuclear defective dicubane azide-bridged cobalt(II) complex
2013
Abstract The new tetranuclear cobalt(II) complex with formula [Co4(N3)8(4,5-diazafluoren-9-one)4] (1) is reported. Complex 1 is a cobalt(II) defective dicubane azide-bridged compound showing only azido bridging ligands in the μ1,1– and μ1,1,1– coordination modes. The magnetic properties of 1 are reported. Magnetic susceptibility measurements indicate ferromagnetic coupling. The magnetic data have been fitted to 2 K by considering two different superexchange coupling constants. The out-of-phase signal χM″ displays frequency-dependence below approximately 9 K.
Orbital Rotations induced by Charges of Polarons and Defects in Doped Vanadates
2020
We explore the competiton of doped holes and defects that leads to the loss of orbital order in vanadate perovskites. In compounds such as La$_{1-{\sf x}}$Ca$_{\,\sf x}$VO$_3$ spin and orbital order result from super-exchange interactions described by an extended three-orbital degenerate Hubbard-Hund model for the vanadium $t_{2g}$ electrons. Long-range Coulomb potentials of charged Ca$^{2+}$ defects and $e$-$e$ interactions control the emergence of defect states inside the Mott gap. The quadrupolar components of the Coulomb fields of doped holes induce anisotropic orbital rotations of degenerate orbitals. These rotations modify the spin-orbital polaron clouds and compete with orbital rotat…
NMR study of magnetic order, metamagnetic transitions, and low-temperature spin freezing in Ca3Co2O6
2011
We report on a (59)Co NMR investigation of the trigonal cobaltate Ca(3)Co(2)O(6) carried out on a single crystal, providing precise determinations of the electric field gradient and chemical shift tensors, and of the internal magnetic fields at the nonmagnetic Co I sites, unavailable from former studies on powders. The magnetic-field-induced ferri-and ferromagnetic phases at intermediate temperature (e.g., 10 K) are identified by distinct internal fields, well accounted for by purely dipolar interactions. The vanishing transferred hyperfine field at the Co I site indicates that the Co(3+) (I) orbitals do not participate in the intrachain superexchange, in disagreement with a previous theore…
High-valent bis(oxo)-bridged dinuclear manganese oxamates: Synthesis, crystal structures, magnetic properties, and electronic structure calculations …
2007
[EN] Two novel bis(oxo)-bridged dinuclear manganese(IV) complexes with the binucleating ligand o-phenylenebis(oxamate) (opba), formulated as (Me4N)(4)[Mn2O2(opba)(2)] (1a) and (Me4N)(2)(Ph4P)(2)[Mn2O2(opba)(2)] (.) 8H(2)O (1b), have been synthesized and characterized structurally and magnetically. Like the parent complex (Ph4P)(4)[Mn2O2(opba)(2)] (.) 4H(2)O (1c), they possess unique Mn-2(mu-O)(2) bridging cores with two additional o-phenylenediamidate bridges which lead to exceptionally short Mn-Mn distances (2.63-2.67 angstrom) and fairly bent Mn-O-Mn angles (93.8-95.5 degrees). Complexes 1a-c show a moderate to strong antiferromagnetic coupling between the two high-spin Mn-IV ions through…
Semiconductive and Magnetic One-Dimensional Coordination Polymers of Cu(II) with Modified Nucleobases
2013
Four new copper(II) coordination complexes, obtained by reaction of CuX2 (X = acetate or chloride) with thymine-1-acetic acid and uracil-1-propionic acid as ligands, of formulas [Cu(TAcO)2(H2O)4]·4H2O (1), [Cu(TAcO)2(H2O)2]n (2), [Cu3(TAcO)4(H2O)2(OH)2]n·4H2O (3), and [Cu3(UPrO)2Cl2(OH)2(H2O)2]n (4) (TAcOH = thymine-1-acetic acid, UPrOH = uracil-1-propionic acid) are described. While 1 is a discrete complex, 2-4 are one-dimensional coordination polymers. Complexes 2-4 present dc conductivity values between 10(-6) and 10(-9) S/cm(-1). The magnetic behavior of complex 2 is typical for almost isolated Cu(II) metal centers. Moderate-weak antiferromagnetic interactions have been found in complex…
Bioinspired manganese(II) complexes with a clickable ligand for immobilisation on a solid support.
2014
International audience; Clickable ligands like N,N′-bis((pyridin-2-yl)methyl)prop-2-yn-1-amine (L1) and N-((1-methyl-1H-imidazol-2-yl)methyl)-N-(pyridin-2-ylmethyl)prop-2-yn-1-amine (L2) have been used to synthesise a series of manganese(II) complexes for grafting onto appropriate solid supports. These ligands mimic the 2-His-1-carboxylate facial chelation present in the active site of the manganese-dependent dioxygenase (MndD), while the alkyne side function allows grafting of the ligand onto an azido-functionalised support using “click chemistry” methodologies. Such synthetic analogues of the MndD crystallise in the solid state as double halide or pseudohalide-bridged dinuclear manganese(…
Magnetism of metallacrown single-molecule magnets: From a simplest model to realistic systems
2018
Electronic and magnetic properties of molecular nanomagnets are determined by competing energy scales due to the crystal field splitting, the exchange interactions between transition metal atoms, and relativistic effects. We present a comprehensive theory embracing all these phenomena based on first-principles calculations. In order to achieve this goal, we start from the ${\mathrm{FeNi}}_{4}$ cluster as a paradigm. The system can be accurately described on the ab initio level yielding all expected electronic states in a range of multiplicities from 1 to 9, with a ferromagnetic ground state. By adding the spin-orbit coupling between them we obtain the zero-field splitting. This allows to in…