Calculation of model Hamiltonian parameters for LaMnO_3 using maximally localized Wannier functions

Maximally localized Wannier functions (MLWFs) based on Kohn-Sham band-structures provide a systematic way to construct realistic, materials specific tight-binding models for further theoretical analysis. Here, we construct MLWFs for the Mn e_g bands in LaMnO_3, and we monitor changes in the MLWF matrix elements induced by different magnetic configurations and structural distortions. From this we obtain values for the local Jahn-Teller and Hund's rule coupling strength, the hopping amplitudes between all nearest and further neighbors, and the corresponding reduction due to the GdFeO_3-type distortion. By comparing our results with commonly used model Hamiltonians for manganites, where electrons can hop between two "e_g-like" orbitals located on each Mn site, we find that the most crucial limitation of such models stems from neglecting changes in the underlying Mn(d)-O(p) hybridization.Comment: 15 pages, 11 figures, 3 table

Structural distortions and model Hamiltonian parameters: from LSDA to a tight-binding description of LaMnO_3

The physics of manganites is often described within an effective two-band tight-binding (TB) model for the Mn e_g electrons, which apart from the kinetic energy includes also a local "Hund's rule" coupling to the t_{2g} core spin and a local coupling to the Jahn-Teller (JT) distortion of the oxygen octahedra. We test the validity of this model by comparing the energy dispersion calculated for the TB model with the full Kohn-Sham band-structure calculated within the local spin-density approximation (LSDA) to density functional theory. We analyze the effect of magnetic order, JT distortions, and "GdFeO_3-type" tilt-rotations of the oxygen octahedra. We show that the hopping amplitudes are independent of magnetic order and JT distortions, and that both effects can be described with a consistent set of model parameters if hopping between both nearest and next-nearest neighbors is taken into account. We determine a full set of model parameters from the density functional theory calculations, and we show that both JT distortions and Hund's rule coupling are required to obtain an insulating ground state within LSDA. Furthermore, our calculations show that the "GdFeO_3-type" rotations of the oxygen octahedra lead to a substantial reduction of the hopping amplitudes but to no significant deviation from the simple TB model.Comment: replaced with final (published) version with improved presentatio

Origin of ferroelectricity in the multiferroic barium fluorides BaMF4

We present a first principles study of the series of multiferroic barium fluorides with the composition BaMF4, where M is Mn, Fe, Co, or Ni. We discuss trends in the structural, electronic, and magnetic properties, and we show that the ferroelectricity in these systems results from the "freezing in" of a single unstable polar phonon mode. In contrast to the case of the standard perovskite ferroelectrics, this structural distortion is not accompanied by charge transfer between cations and anions. Thus, the ferroelectric instability in the multiferroic barium fluorides arises solely due to size effects and the special geometrical constraints of the underlying crystal structure.Comment: 8 pages, 6 figures, 3 table

Electronic Structure of Cu_(1-x)Ni_xRh_2S_4 and CuRh_2Se_4: Band Structure Calculations, X-ray Photoemission and Fluorescence Measurements

The electronic structure of spinel-type Cu_(1-x)Ni_xRh_2S_4 (x = 0.0, 0.1, 0.3, 0.5, 1.0) and CuRh_2Se_4 compounds has been studied by means of X-ray photoelectron and fluorescent spectroscopy. Cu L_3, Ni L_3, S L_(2,3) and Se M_(2,3) X-ray emission spectra (XES) were measured near thresholds at Beamline 8.0 of the Lawrence Berkeley Laboratory's Advanced Light Source. XES measurements of the constituent atoms of these compounds, reduced to the same binding energy scale, are found to be in excellent agreement with XPS valence bands. The calculated XES spectra which include dipole matrix elements show that the partial density of states reproduce experimental spectra quite well. States near the Fermi level (E_F) have strong Rh d and S(Se) p character in all compounds. In NiRh_2S_4 the Ni 3d states contribute strongly at E_F, whereas in both Cu compounds the Cu 3d bands are only ~1 eV wide and centered ~2.5 eV below E_F, leaving very little 3d character at E_F. The density of states at the Fermi level is less in NiRh_2S_4 than in CuRh_2S_4. This difference may contribute to the observed decrease, as a function of Ni concentration, in the superconducting transition temperature in Cu_(1-x)Ni_xRh_2S_4. The density of states of the ordered alloy Cu_(1/2)Ni_(1/2)Rh_2S_4 shows behavior that is more ``split-band''-like than ``rigid band''-like.Comment: 7 pages of text, 11 trailing figures, updated to fix faulty postscript in Fig.

An experimental and computational investigation of structure and magnetism in pyrite Co1−x_{1-x}Fex_xS2_2: Chemical bonding and half-metallicity

Bulk samples of the pyrite chalcogenide solid solutions Co$_{1-x}$Fe$_x$S$_2$ 0 <= x <= 0.5, have been prepared and their crystal structures and magnetic properties studied by X-ray diffraction and SQUID magnetization measurements. Across the solution series, the distance between sulfur atoms in the persulfide (S$_2^{2-}$) unit remains nearly constant. First principles electronic structure calculations using experimental crystal structures as inputs point to the importance of this constant S-S distance, in helping antibonding S-S levels pin the Fermi energy. In contrast hypothetical rock-salt CoS is not a good half metal, despite being nearly isostructural and isoelectronic. We use our understanding of the Co$_{1-x}$Fe$_x$S$_2$ system to make some prescriptions for new ferromagnetic half-metals.Comment: 8 pages including 9 figure

Electric-field switchable magnetization via the Dzyaloshinskii-Moriya interaction: FeTiO_3 versus BiFeO_3

In this article we review and discuss a mechanism for coupling between electric polarization and magnetization that can ultimately lead to electric-field switchable magnetization. The basic idea is that a ferroelectric distortion in an antiferromagnetic material can "switch on" the Dzyaloshinskii-Moriya interaction which leads to a canting of the antiferromagnetic sublattice magnetizations, and thus to a net magnetization. This magnetization M is coupled to the polarization P via a trilinear free energy contribution of the form P(M x L), where L is the antiferromagnetic order parameter. In particular, we discuss why such an invariant is present in R3c FeTiO_3 but not in the isostructural multiferroic BiFeO_3. Finally, we construct symmetry groups that in general allow for this kind of ferroelectrically-induced weak ferromagnetism.Comment: 15 pages, 3 images, to appear in J. Phys: Condens. Matter Focus Issue on Multiferroic

First principles study of the multiferroics BiFeO3_{3}, Bi2_{2}FeCrO6_{6}, and BiCrO3_{3}: Structure, polarization, and magnetic ordering temperature

We present results of an {\it ab initio} density functional theory study of three bismuth-based multiferroics, BiFeO$_{3}$, Bi$_{2}$FeCrO$_{6}$, and BiCrO$_{3}$. We disuss differences in the crystal and electronic structure of the three systems, and we show that the application of the LDA+$U$ method is essential to obtain realistic structural parameters for Bi$_{2}$FeCrO$_{6}$. We calculate the magnetic nearest neighbor coupling constants for all three systems and show how Anderson's theory of superexchange can be applied to explain the signs and relative magnitudes of these coupling constants. From the coupling constants we then obtain a mean-field approximation for the magnetic ordering temperatures. Guided by our comparison of these three systems, we discuss the possibilities for designing a multiferroic material with large magnetization above room temperature.Comment: 8 Pages, 4 Figure

Killer acquisitions

This paper argues incumbent firms may acquire innovative targets solely to discontinue the target’s innovation projects and preempt future competition. We call such acquisitions “killer acquisitions.” We develop a model illustrating this phenomenon. Using pharmaceutical industry data, we show that acquired drug projects are less likely to be developed when they overlap with the acquirer’s existing product portfolio, especially when the acquirer’s market power is large due to weak competition or distant patent expiration. Conservative estimates indicate 5.3 percent to 7.4 percent of acquisitions in our sample are killer acquisitions. These acquisitions disproportionately occur just below thresholds for antitrust scrutiny