Thermodynamic Properties of Ferromagnetic Mott- Insulators GaV4S8

We present the results of the magnetic and specific heat measurements on V4 tetrahedral-cluster compound GaV4S8 between 2 to 300K. We find two transitions related to a structural change at 42K followed by ferromagnetic order at 12K on cooling. Remarkably similar properties were previously reported for the cluster compounds of Mo4. These compounds show an extremely high density of low energy excitations in their electronic properties. We explain this behavior in a cluster compound as due to the reduction of coulomb repulsion among electrons that occupy highly degenerate orbits of different clusters.Comment: To be publish in Physica

Exchange bias effect in alloys and compounds

The phenomenology of exchange bias effects observed in structurally single-phase alloys and compounds but composed of a variety of coexisting magnetic phases such as ferromagnetic, antiferromagnetic, ferrimagnetic, spin-glass, cluster-glass and disordered magnetic states are reviewed. The investigations on exchange bias effects are discussed in diverse types of alloys and compounds where qualitative and quantitative aspects of magnetism are focused based on macroscopic experimental tools such as magnetization and magnetoresistance measurements. Here, we focus on improvement of fundamental issues of the exchange bias effects rather than on their technological importance

Ferrimagnetism of dilute Ising antiferromagnets

It is shown that nearest-neighbor antiferromagnetic interactions of identical Ising spins on imbalanced bipartite lattice and imbalanced bipartite hierarchical fractal result in ferrimagnetic order instead of antiferromagnetic one. On some crystal lattices dilute Ising antiferromagnets may also become ferrimagnets due to the imbalanced nature of the magnetic percolation cluster when it coexists with the percolation cluster of vacancies. As evidenced by the existing experiments on $Fe_pZn_{1-p}F_2$, such ferrimagnetism is inherent property of bcc lattice so thermodynamics of these compounds at low $p$ can be similar to that of antiferromagnet on imbalanced hierarchical fractal.Comment: 6 pages, 4 figure

Nucleophilicity/Electrophilicity Excess in Analyzing Molecular Electronics

Intramolecular electron transfer capability of all metal aromatic and anti-aromatic aluminum cluster compounds is studied in terms of density functional theory based global and local reactivity descriptors. This study will provide important inputs towards the fabrication of the material required for molecular electronics.Comment: 21 pages, 6 figures, 13 table

Threshold electronic structure at the oxygen K edge of 3d transition metal oxides: a configuration interaction approach

It has been generally accepted that the threshold structure observed in the oxygen K edge X-ray absorption spectrum in 3d transition metal oxides represents the electronic structure of the 3d transition metal. There is, however, no consensus about the correct description. We present an interpretation, which includes both ground state hybridization and electron correlation. It is based on a configuration interaction cluster calculation using a MO6 cluster. The oxygen K edge spectrum is calculated by annihilating a ligand hole in the ground state and is compared to calculations representing inverse photoemission experiments in which a 3d transition metal electron is added. Clear differences are observed related to the amount of ligand hole created in the ground state. Two "rules" connected to this are discussed. Comparison with experimental data of some early transition metal compounds is made and shows that this simple cluster approach explains the experimental features quite well.Comment: 10 pages, submitted to Phys. Rev. B, tried to make a better PS file

Magnetism of CuX2 frustrated chains (X = F, Cl, Br): the role of covalency

Periodic and cluster density-functional theory (DFT) calculations, including DFT+U and hybrid functionals, are applied to study magnetostructural correlations in spin-1/2 frustrated chain compounds CuX2: CuCl2, CuBr2, and a fictitious chain structure of CuF2. The nearest-neighbor and second-neighbor exchange integrals, J1 and J2, are evaluated as a function of the Cu-X-Cu bridging angle, theta, in the physically relevant range 80-110deg. In the ionic CuF2, J1 is ferromagnetic for theta smaller 100deg. For larger angles, the antiferromagnetic superexchange contribution becomes dominant, in accord with the Goodenough-Kanamori-Anderson rules. However, both CuCl2 and CuBr2 feature ferromagnetic J1 in the whole angular range studied. This surprising behavior is ascribed to the increased covalency in the Cl and Br compounds, which amplifies the contribution from Hund's exchange on the ligand atoms and renders J1 ferromagnetic. At the same time, the larger spatial extent of X orbitals enhances the antiferromagnetic J2, which is realized via the long-range Cu-X-X-Cu paths. Both, periodic and cluster approaches supply a consistent description of the magnetic behavior which is in good agreement with the experimental data for CuCl2 and CuBr2. Thus, owing to their simplicity, cluster calculations have excellent potential to study magnetic correlations in more involved spin lattices and facilitate application of quantum-chemical methods

Inter-cluster reactivity of Metallo-aromatic and anti-aromatic Compounds and Their Applications in Molecular Electronics: A Theoretical Investigation

Local reactivity descriptors such as the condensed local softness and Fukui function have been employed to investigate the inter-cluster reactivity of the metallo-aromatic (Al4Li- and Al4Na-) and anti-aromatic (Al4Li4 and Al4Na4) compounds. We use the concept of group softness and group Fukui function to study the strength of the nucleophilicity of the Al4 unit in these compounds. Our analysis shows that the trend of nucleophilicity of the Al4 unit in the above clusters is as follows; Al4Li- > Al4Na- > Al4Li4 > Al4Na 4 For the first time we have used the reactivity descriptors to show that these clusters can act as electron donating systems and thus can be used as a molecular cathode.Comment: 23 pages, 1 figure and 1 table of conten

Spectral functions for strongly correlated 5f-electrons

We calculate the spectral functions of model systems describing 5f-compounds adopting Cluster Perturbation Theory. The method allows for an accurate treatment of the short-range correlations. The calculated excitation spectra exhibit coherent 5f bands coexisting with features associated with local intra-atomic transitions. The findings provide a microscopic basis for partial localization. Results are presented for linear chains.Comment: 10 Page