Disproportionation, metal-insulator transition, and critical interaction strength in Na(1/2)CoO2

Charge disproportionation (CD) and spin differentiation in Na(1/2)CoO2 are studied using the correlated band local-density approximation + Hubbard U (LDA+U) approach. The simultaneous CD and gap opening seen previously is followed in detail through a first-order charge disproportionation transition 2Co(3.5+)-->Co3++Co4+. Disproportionation in the Co a(g) orbital results in half of the ions (Co3+) becoming electronically and magnetically dead, transforming the quarter-filled a(g) system into a half-filled subsystem that subsequently undergoes the observed charge ordering or metal-insulator transition. Comparing with data in the x approximately 0.3 regime suggests the system has moved into the multiband regime where the effective Coulomb repulsion U-->U(eff)=U/sqrt[3] strongly lessens correlation effects.     

Charge and spin ordering in insulating Na0.5CoO2: effects of correlation and symmetry

Ab initio band theory including correlations due to intra-atomic repulsion is applied to study charge disproportionation and charge and spin ordering in insulating Na0.5CoO2. Various ordering patterns (zigzag and two striped) for four-Co supercells are analyzed before focusing on the observed "out-of-phase stripe" pattern of antiferromagnetic Co4+ spins along charge-ordered stripes. This pattern relieves frustration and shows distinct analogies with the cuprate layers: a bipartite lattice of antialigned spins, with axes at 90degrees angles. Substantial distinctions with cuprates are also discussed, including the tiny gap of a new variant of "charge-transfer" type within the Co 3d system.     

Orbital ordering in LaMnO3 : electron-electron versus electron-lattice interactions

The relative importance of electron-lattice (e-l) and electron-electron (e-e) interactions in ordering orbitals in LaMnO3 is systematically examined within the local-density approximation + Hubbard U approximation of density functional theory. A realistic effective Hamiltonian is derived from novel Wannier state analysis of the electronic structure. Surprisingly, e-l interaction (approximately or = 0.9 eV) alone is found insufficient to stabilize the orbital ordered state. On the other hand, e-e interaction (approximately or = 1.7 eV) not only induces orbital ordering, but also greatly facilitates the Jahn-Teller distortion via enhanced localization. Further experimental means to quantify the competition between these two mechanisms are proposed.     

Electron correlation and fermi surface topology of NaxCoO2

The electronic structure of NaxCoO2 revealed by recent photoemission experiments shows important deviations from band theory predictions. The six small Fermi surface pockets predicted by local-density approximation calculations have not been observed as the associated e'(g) band fails to cross the Fermi level for a wide range of sodium doping concentration x. In addition, significant bandwidth renormalizations of the t(2g) complex have been observed. We show that these discrepancies are due to strong electronic correlations by studying the multiorbital Hubbard model in the Hartree-Fock and strong-coupling Gutzwiller approximation. The quasiparticle dispersion and the Fermi surface topology obtained in the presence of strong local Coulomb repulsion are in good agreement with experiments.     

Static magnetic order in metallic K0.49CoO2

By means of muon-spin spectroscopy, we have found that K0.49CoO2 crystals undergo successive magnetic transitions from a high-T paramagnetic state to a magnetic ordered state below 60 K and then to a second ordered state below 16 K, even though K0.49CoO2 is metallic at least down to 4 K. An isotropic magnetic behavior and wide internal-field distributions suggest the formation of a commensurate helical spin density wave (SDW) state below 16 K, while a linear SDW state is likely to exist above 16 K. It was also found that exhibits a further transition at 150 K presumably due to a change in the spin state of the Co ions. Since the dependence of the internal-field below 60 K was similar to that for Na0.5CoO2, this suggests that magnetic order is more strongly affected by the Co valence than by the interlayer distance or interaction and/or the charge ordering.     

Charge ordering and magnetopolarons in Na0.82CoO2

Using spectral ellipsometry, we measured the dielectric function of a Na(0.82(2))CoO2 crystal that exhibits bulk antiferromagnetism with T(N)=19.8 K. We identify two prominent transitions as a function of temperature. The first one at 280 K involves marked changes of the electronic and lattice responses that are indicative of charge ordering in the CoO2 layers. The second transition occurs around T(N)=19.8 K and reveals sizable spin-charge coupling. The data are discussed in terms of charge ordering and formation of magnetopolarons due to a charge-induced spin-state transition of adjacent Co3+ ions.     

Orbital-ordering transition in Sr2VO4

Temperature-dependent dc susceptibility and x-ray powder diffraction on a pure tetragonal sample of Sr(2)VO(4) show an antiferromagnetic orbital-ordering transition at T(oo) = 97 K, in which the occupied orbitals lie along the c axis. The unusual broadening of the x-ray Bragg peaks throughout the orbital-ordering transition temperature region indicates that this process occurs in stages, and the onset of short-range orbital ordering occurs at T(1) approximately 122 K. The study of the order parameter associated with this transition by analyzing the spontaneous strain results in a critical exponent beta = 0.35(2) consistent with 3D Heisenberg behavior. These results experimentally confirm the orbital-ordering state in Sr(2)VO(4) predicted by first-principles calculations using combinations of the local-density approximation and the GW method.     

59Co NMR evidence for charge ordering below T_(CO) approximately 51 K in Na0.5CoO2

The CoO2 layers in NaxCoO2 may be viewed as a spin S=1/2 triangular-lattice doped with charge carriers. The underlying physics of the cobaltates is very similar to that of the high T_(c) cuprates. We will present unequivocal 59Co NMR evidence that below T_(CO) approximately 51 K, the insulating ground state of the itinerant antiferromagnet Na0.5CoO2 (T_(N) approximately 86 K) is induced by charge ordering.     

Electron — positron quantum droplets

A new physical object, electron-positron quantum droplet, is suggested. Structure, stability and dynamics of such objects are discussed. The analysis is based on the non-relativistic self-consistent local-density approximation. An essential role of many-body effects in the formation of the droplets is demonstrated. Their properties are compared with the known physical objects such as metal clusters and clusters of excitons in a solid.     

Non-local exchange correlation energy in quasi-two-dimensional electron layers

We introduce a simple, non-local approximation for the exchange-correlation energy of an inhomogeneous electron gas. This approximation is shown to be quantitatively accurate in several important limiting cases. The method is used to calculate the non-local exchange-correlation energy for density distributions representing quasi-two-dimensional electron layers. These energies are compared to the widely used three-dimensional local-density approximation and suggest that the latter approximation may contain errors on the order of 10–30% for layer profiles typical of real systems.     

Electronic texture of the thermoelectric oxide Na0.75CoO2

From 59Co and 23Na NMR, we demonstrate the impact of the Na+ vacancy ordering on the cobalt electronic states in Na0.75CoO2: at long time scales, there is neither a disproportionation into 75% Co3+ and 25% Co4+ states, nor a mixed-valence metal with a uniform Co3.25+ state. Instead, the system adopts an intermediate configuration in which 30% of the lattice sites form an ordered pattern of localized Co3+ states. Above 180 K, an anomalous mobility of specific Na+ sites is found to coexist with this electronic texture, suggesting that the formation of the latter may contribute to stabilizing the Na+ ordering. Control of the ion doping in these materials thus appears to be crucial for fine-tuning of their thermoelectric properties.     

Strong Coulomb correlation effects in ZnO

The electronic structure, band parameters, and optical spectra of wurtzite-type ZnO were studied by first-principles calculations within different approximations of the density functional theory. The local-density approximation underestimates the band gap, the energy levels of the Zn-3d states, the band dispersion, the crystal-field splitting, the spin-orbit interaction, and location of peaks in the optical spectra. The generalized-gradient approximation slightly corrects the discrepancies with the experimental findings and it shows good agreement for the optical spectra with experimental data at energies 10-20 eV for E⊥c. Studies within the local-density approximation with the multiorbital mean-field Hubbard potential show that strong Coulomb correlations are in operation. From effective mass calculations it is found that holes are much heavier and more anisotropic than the conduction-band electrons in ZnO.     

Low to high spin-state transition induced by charge ordering in antiferromagnetic YBaCo2O5

The oxygen-deficient double perovskite YBaCo2O5, containing corner-linked CoO5 square pyramids as principal building units, undergoes a paramagnetic to antiferromagnetic spin ordering at 330 K. This is accompanied by a tetragonal to orthorhombic distortion. Below 220 K orbital ordering and long-range Co(2+)/Co(3+) charge ordering occur as well as a change in the Co2+ spin state from low to high spin. This transition is shown to be very sensitive to the oxygen content of the sample. To our knowledge this is the first observation of a spin-state transition induced by long-range orbital and charge ordering.     

Photoabsorption spectra of Na(+)(n) clusters: thermal line-broadening mechanisms

Photoabsorption cross sections of small sodium cluster cations ( Na(+)(n), n = 3, 5, 7, and 9) were calculated at various temperatures with the time-dependent local-density approximation in conjunction with ab initio molecular dynamics simulations, yielding spectra that agree with measured ones without ad hoc line broadening or renormalization. Three thermal line-broadening mechanisms are revealed: (I) lifting of level degeneracies caused by symmetry-breaking ionic motions, (II) oscillatory shifts of the entire spectrum caused by breathing vibrations, and (III) cluster structural isomerizations.     

Three-dimensional spin fluctuations in Na0.75CoO2

We report polarized- and unpolarized-neutron scattering measurements of magnetic excitations in single-crystal Na0.75CoO2. The data confirm ferromagnetic correlations within the cobalt layers and reveal antiferromagnetic correlations perpendicular to the layers, consistent with an A-type antiferromagnetic ordering. The magnetic modes propagating perpendicular to the layers are sharp, and reach a maximum energy of approximately 12 meV. From a minimal spin-wave model, containing only nearest-neighbor Heisenberg exchange interactions, we estimate the interlayer and intralayer exchange constants to be 12.2+/-0.5 meV and -6+/-2 meV, respectively. We conclude that the magnetic fluctuations in Na0.75CoO2 are highly three dimensional.     

Electronic structure and superconductivity of europium

We have calculated the electronic structure of Eu for the bcc, hcp, and fcc crystal structures for volumes near equilibrium up to a calculated 90 GPa pressure using the augmented-plane-wave method in the local-density approximation. The frozen-core approximation was used with a semi-empirical shift of the f-states energies in the radial Schrödinger equation to move the occupied 4f valence states below the Γ₁ energy and into the core. This shift of the highly localized f-states yields the correct europium phase ordering with lattice parameters and bulk moduli in good agreement with experimental data. The calculated superconductivity properties under pressure for the bcc and hcp structures are also found to agree with and follow a T_c trend similar to recent measurement by Debessai et al. [1].     

Charge-orbital ordering and Verwey transition in magnetite

Local density approximation + Hubbard U (LDA + U) band structure calculations reveal that magnetite (Fe3O4) forms an insulating charge-orbital-ordered state below the Verwey transition temperature. The calculated charge ordering is in good agreement with that inferred from recent experiments. We found an associated t(2g) orbital ordering on the octahedral Fe2+ sublattice. Such an orbital ordering results primarily from the on-site Coulomb interaction. This finding unravels such fundamental issues about the Verwey transition as the mechanism for the charge ordering and for the formation of the insulating gap, as well as the nonobedience of the Anderson's criterion for the charge ordering.     

Electronic structure of nearly ferromagnetic compound HfZn2

The electronic structure of HfZn₂ has been studied based on the density functional theory within the local-density approximation. The calculation indicates that HfZn₂ shows ferromagnetic instability. Large enhancement of the static susceptibility over its non-interacting value is found due to a peak in the density of states at the Fermi level.     

Structural stability and specific-heat coefficient of Yb

The linear muffin-tin-orbital method within the atomic-sphere approximation is used to calculate the structural energy differences and specific-heat coefficient of ytterbium metal. It has been shown that while nonlocal exchange corrections to the local-density approximation play almost no role for the structural energy differences, specific-heat coefficient values are correctly predicted only when these contributions are taken into account.     

Fermi surface of NaxCoO2

Doping evolution of the Fermi surface topology of Na(x)CoO(2) is studied systematically. Both local density approximation (LDA) and local spin density approximation (LSDA) predict a large Fermi surface as well as small hole pockets for doping levels x approximately 0.5. In contrast, the hole pockets are completely absent for all doping levels within LSDA+U. More importantly, we find no violation of Luttinger's rule in this system. The measured Fermi surface of Na(0.7)CoO(2) can be explained by its half-metallic behavior and agrees with our LSDA+U calculations.