Orbital structure and magnetic ordering in stoichiometric and doped crednerite CuMnO2

The exchange interactions and magnetic structure in layered system CuMnO2 (mineral crednerite) and in nonstoichiometric system Cu1.04Mn0.96O2, with triangular layers distorted due to orbital ordering of the Mn3+ ions, are studied by ab-initio band-structure calculations, which were performed within the GGA+U approximation. The exchange interaction parameters for the Heisenberg model within the Mn-planes and between the Mn-planes were estimated. We explain the observed in-plane magnetic structure by the dominant mechanism of the direct d-d exchange between neighboring Mn ions. The superexchange via O ions, with 90 degree Mn-O-Mn bonds, plays less important role for the in-plane exchange. The interlayer coupling is largely dominated by one exchange path between the half-filled 3z^2-r^2 orbitals of Mn3+. The change of interlayer coupling from antiferromagnetic in pure CuMnO2 to ferromagnetic in doped material is also explained by our calculations

Electronic structure of V4_4O7_7: charge ordering, metal-insulator transition and magnetism

The low and high-temperature phases of V$_4$O$_7$ have been studied by \textit{ab initio} calculations. At high temperature, all V atoms are electronically equivalent and the material is metallic. Charge and orbital ordering, associated with the distortions in the V pseudo-rutile chains, occur below the metal-insulator transition. Orbital ordering in the low-temperature phase, different in V$^{3+}$ and V$^{4+}$ chains, allows to explain the distortion pattern in the insulating phase of V$_4$O$_7$. The in-chain magnetic couplings in the low-temperature phase turn out to be antiferromagnetic, but very different in the various V$^{4+}$ and V$^{3+}$ bonds. The V$^{4+}$ dimers formed below the transition temperature form spin singlets, but V$^{3+}$ ions, despite dimerization, apparently participate in magnetic ordering.Comment: 10 pages, 6 figures, 2 table

Role of local geometry in spin and orbital structure of transition metal compounds

We analyze the role of local geometry in the spin and orbital interaction in transition metal compounds with orbital degeneracy. We stress that the tendency observed for the most studied case (transition metals in O$_6$ octahedra with one common oxygen -- common corner of neighboring octahedra and with $\sim 180^{\circ}$ metal--oxygen--metal bonds), that ferro-orbital ordering renders antiferro-spin coupling, and, {\it vice versa}, antiferro-orbitals give ferro-spin ordering, is not valid in general case, in particular for octahedra with common edge and with $\sim 90^{\circ}$ M--O--M bonds. Special attention is paid to the ``third case'', neighboring octahedra with common face (three common oxygens) -- the case practically not considered until now, although there are many real systems with this geometry. Interestingly enough, the spin--orbital exchange in this case turns out to be to be simpler and more symmetric than in the first two cases. We also consider, which form the effective exchange takes for different geometries in case of strong spin--orbit coupling.Comment: 31 pages, 9 figures, submitted to JET

Rhodium Doped Manganites : Ferromagnetism and Metallicity

The possibility to induce ferromagnetism and insulator to metal transitions in small A site cation manganites Ln_{1-x}Ca_xMnO_3 by rhodium doping is shown for the first time. Colossal magnetoresistance (CMR) properties are evidenced for a large compositional range (0.35 \leq x < 0.60). The ability of rhodium to induce such properties is compared to the results obtained by chromium and ruthenium doping. Models are proposed to explain this behavior.Comment: 11 pages, 8 figure

Spin-state transition in LaCoO3: direct neutron spectroscopic evidence of excited magnetic states

A gradual spin-state transition occurs in LaCoO3 around T~80-120 K, whose detailed nature remains controversial. We studied this transition by means of inelastic neutron scattering (INS), and found that with increasing temperature an excitation at ~0.6 meV appears, whose intensity increases with temperature, following the bulk magnetization. Within a model including crystal field interaction and spin-orbit coupling we interpret this excitation as originating from a transition between thermally excited states located about 120 K above the ground state. We further discuss the nature of the magnetic excited state in terms of intermediate-spin (IS, S=1) vs. high-spin (HS, S=2) states. Since the g-factor obtained from the field dependence of the INS is g~3, the second interpretation looks more plausible.Comment: 10 pages, 4 figure

Structural transition in AuAgTe4 under pressure

Gold is inert and forms very few compounds. One of the most interesting of those is calaverite AuTe2, which has incommensurate structure and which becomes superconducting when doped or under pressure. There exist a "sibling" of AuTe2 the mineral sylvanite AuAgTe4, which properties are almost unknown. In sylvanite Au and Ag ions are ordered in stripes, and Te6 octahedra around metals are distorted in such a way that Ag becomes linearly coordinated, what is typical for Ag^{1+}, whereas Au is square coordinated - it is typical for d^8 configurations, i.e. one can assign to Au the valence 3+. Our theoretical study shows that at pressure P_C ~ 5 GPa there should occur in it a structural transition such that above this critical pressure Te6 octahedra around Au and Ag become regular and practically identical. Simultaneously Te-Te dimers, existing at P = 0 GPa, disappear, and material from a bad metal becomes a usual metal with predominantly Te 5p states at the Fermi energy. We expect that, similar to AuTe2, AuAgTe4 should become superconducting above P_C.Comment: 8 pages, 4 figure

Microphase separation in Pr0.67Ca0.33MnO3 by small angle neutron scattering

We have evidenced by small angle neutron scattering at low temperature the coexistence of ferromagnetism (F) and antiferromagnetism (AF) in Pr0.67Ca0.33MnO3. The results are compared to those obtained in Pr0.80Ca0.20MnO3 and Pr0.63Ca0.37MnO3, which are F and AF respectively. Quantitative analysis shows that the small angle scattering is not due to a mesoscopic mixing but to a nanoscopic electronic and magnetic ''red cabbage'' structure, in which the ferromagnetic phase exists in form of thin layers in the AF matrix (stripes or 2D ''sheets'').Comment: 4 figure

Giant positive magnetoresistance in metallic VOx thin films

We report on giant positive magnetoresistance effect observed in VOx thin films, epitaxially grown on SrTiO3 substrate. The MR effect depends strongly on temperature and oxygen content and is anisotropic. At low temperatures its magnitude reaches 70% in a magnetic field of 5 T. Strong electron-electron interactions in the presence of strong disorder may qualitatively explain the results. An alternative explanation, related to a possible magnetic instability, is also discussed.Comment: 4 pages, 5 figures included in the text, references update

Crystal field splitting in correlated systems with the negative charge-transfer gap

Special features of the crystal field splitting of $d-$levels in the transition metal compounds with the small or negative charge-transfer gap $\Delta_{CT}$ are considered. We show that in this case the Coulomb term and the covalent contribution to the $t_{2g} - e_g$ splitting have different signs. In order to check the theoretical predictions we carried out the ab-initio band structure calculations for Cs$_2$Au$_2$Cl$_6$, in which the charge-transfer gap is negative, so that the $d-$electrons predominantly occupy low-lying bonding states. For these states the $e_g$-levels lie below $t_{2g}$ ones, which demonstrates that at least in this case the influence of the $p-d$ covalency on the total value of the crystal field splitting is stronger than the Coulomb interaction (which would lead to the opposite level order). We also show that the states in conduction band are made predominantly of $p-$states of ligands (Cl), with small admixture of $d-$states of Au