P. Weinberger

Fully relativistic calculation of magnetic properties of Fe, Co, and Ni adclusters on Ag(100)

We present first-principles calculations of the magnetic moments and magnetic anisotropy energies of small Fe, Co, and Ni clusters on top of a Ag(100) surface as well as the exchange-coupling energy between two single adatoms of Fe or Co on Ag(100). The calculations are performed fully relativistically using the embedding technique within the Korringa-Kohn-Rostoker method. The magnetic anisotropy and the exchange-coupling energies are calculated by means of the force theorem. In the case of adatoms and dimers of iron and cobalt we obtain enhanced spin moments and, especially, unusually large orbital moments, while for nickel our calculations predict a complete absence of magnetism. For larger clusters, the magnitudes of the local moments of the atoms in the center of the cluster are very close to those calculated for the corresponding monolayers. Similar to the orbital moments, the contributions of the individual atoms to the magnetic anisotropy energy strongly depend on the position, hence, on the local environment of a particular atom within a given cluster. We find strong ferromagnetic coupling between two neighboring Fe or Co atoms and a rapid, oscillatory decay of the exchange-coupling energy with increasing distance between these two adatoms.

catena-[μ-Tris(1,2-bis(tetrazol-1-yl)ethane-N4,N4′)iron(II)] bis(tetrafluoroborate): synthesis, structure, spectroscopic and magnetic characterization of a chain-type coordination polymer spin-crossover compound

In analogy to a common synthesis of 1-substituted 5-H tetrazoles (Tetrahedron Lett. 36 (1995)1759; Beloruss. Gos. Univ., Minsk, USSR. Khim. Geterotsikl. Soedin. 11 (1985) 1521; Beloruss. Gos. Univ., Minsk, USSR. Khim. Geterotsikl. Soedin. 1 (1991) 66; BGU, Belarus. Vestsi Akad. Navuk Belarusi, Ser. Khim. Navuk 1 (1992) 73), the new bidentate ligand 1,2-bis(tetrazol-1-yl)ethane [endi] was synthesized and characterized by X-ray diffraction, NMR, IR and UV–Vis spectroscopy. By using iron(II) tetrafluoroborate hexahydrate the complexation with this ligand yields a 1-dimensional linear coordination polymer similar to the recently published chain compound (Inorg. Chem. 39 (2000) 1891) exhibiting a thermally induced spin-crossover phenomenon. Similar to the 1,2-bis(tetrazol-1-yl)propane-bridged compound, our 1,2-bis(tetrazol-1-yl)ethane-bridged compound shows a gradual spin transition, but the spin-crossover temperature T1/2≈140 K is found to be 10 K above the other T1/2. The T1/2 was determined by temperature-dependent 57Fe-Mossbauer, far FT-IR and UV–Vis spectroscopy as well as by temperature-dependent magnetic susceptibility measurements. Single crystals of the complex were grown in situ from a solution of the ligand and iron(II) tetrafluoroborate. The X-ray structure determinations of both the high spin as well as the low spin state of the compound revealed a solid state structure, which is comparable to that of catena-[Fe(1,2-bis(tetrazole-1-yl)propane)3](ClO4)2 (Inorg. Chem. 39 (2000) 1891; 2nd TMR-TOSS Meeting, 4th Spin Crossover Family Meeting, Lufthansa Training Center, Seeheim/Germany, April 30–May 2, 1999). Both the 1,2-bis(tetrazol-1-yl)propane-bridged and our compound do not show a thermal hysteresis effect (J. Am. Chem. Soc. 115 (1993) 9810; Inorg. Chim. Acta 37 (1979) 169; Chem. Phys. Lett. 93 (1982) 567). The synthesis of the complex described in the experimental section yielded a fine powdered product being poorly soluble in most common solvents. The single crystal measurements were done with crystals obtained by various diffusion methods. Most of them yielded either thin needles or small hexagonal prism crystals depending on the specific conditions.

Perpendicular magnetism in magnetic multilayer systems

Abstract The main aspects of the fully relativistic spin-polarized Screened Korringa–Kohn–Rostoker (KKR) method for layered systems (systems with only two-dimensional translational symmetry) are reviewed including, e.g., a discussion of the Dirac–Kohn–Sham Hamiltonian, magnetic configurations, the inhomogeneous coherent potential approximation (CPA) applicable to such systems, and a short description of the (classical) magnetic dipole–dipole interaction. Based on this type of approach “perpendicular magnetism” is then discussed in terms of characteristic features frequently encountered in studies of the magnetic anisotropy energy of magnetic multilayer systems such as oscillations or reorientation transitions. For this purpose layer-resolved band energy contributions and their discrete Fourier transformations with respect to characteristic parameters are discussed for a few prominent systems.

Vacancy-induced changes in the electronic structure of transition metal carbides and nitrides: calculation of X-ray photoemission intensities

Starting from KKR-CPA and KKR-GF densities of states and cross-sections within the single-scatterer final-state approximation, X-ray photoemission intensities were calculated for a series of stoichiometric and substoichiometric transition metal carbides and nitrides. For all compounds nonmetal vacancies give rise to an additional peak in the XPS spectra. The theoretical results are compared to several experimental XPS measurements. In most cases very good agreement is found. The discrepancies between theory and experiment are discussed in detail.

Imaging spin-reorientation transitions in consecutive atomic Co layers on Ru(0001)

By means of spin-polarized low-energy electron microscopy, we show that the magnetic easy axis of one to three atomic-layer thick cobalt films on Ru(0001) changes its orientation twice during deposition: One-monolayer and three-monolayer thick films are magnetized in plane, while two-monolayer films are magnetized out of plane. The Curie temperatures of films thicker than one monolayer are well above room temperature. Fully relativistic calculations based on the screened Korringa-Kohn-Rostoker method demonstrate that only for two-monolayer cobalt films does the interplay between strain, surface, and interface effects lead to perpendicular magnetization.

Ab Initio Study of Curie Temperatures of Diluted Magnetic Semiconductors

The Curie temperature of diluted (Ga,Mn)As magnetic semiconductors in the presence of As antisites is studied from first principles. We map total energies associated with rotations of Mn-magnetic moments onto the effective classical Heisenberg Hamiltonian which is treated in the mean-field approximation to find the Curie temperature. The presence of donors strongly reduces the Curie temperature and gives rise to a ground state with a partial disorder of local moments. We show that the observed dependence of the Curie temperature on the Mn concentration indicates that the concentration of As antisites increases with the Mn content.

Ab initio spin dynamics applied to nanoparticles: Canted magnetism of a finite Co chain along a Pt(111) surface step edge

In order to search for the magnetic ground state of surface nanostructures we extended first principles adiabatic spin dynamics to the case of fully relativistic electron scattering. Our method relies on a constrained density functional theory whereby the evolution of the orientations of the spin-moments results from a semi-classical Landau-Lifshitz equation. This approach is applied to a study of the ground state of a finite Co chain placed along a step edge of a Pt(111) surface. As far as the ground state spin orientation is concerned we obtain excellent agreement with the experiment. Furthermore we observe noncollinearity of the atom-resolved spin and orbital moments. In terms of magnetic force theorem calculations we also demonstrate how a reduction of symmetry leads to the existence of canted magnetic states.

Ab initio theories of electric transport in solid systems with reduced dimensions

Abstract Ab initio theories of electric transport in solid systems with reduced dimensions, i.e., systems that at best are characterized by two-dimensional translational invariance, are reviewed in terms of a fully relativistic description of the Kubo–Greenwood equation. As the use of this equation requires concepts such as collinearity and non-collinearity in order to properly define resistivities or resistances corresponding to particular magnetic configurations, respective consequences of the (local) density functional theory are recalled in quite a detailed manner. Furthermore, since theoretical descriptions of solid systems with reduced dimensions require quantum mechanical methods different from bulk systems (three-dimensional periodicity), the so-called Screened Korringa–Kohn–Rostoker (SKKR-) method for layered systems is introduced together with a matching coherent potential approximation (inhomogeneous CPA). The applications shown are mainly meant to illustrate various aspects of electric transport in solid systems with reduced dimensions and comprise not only current-in-plane (CIP) experiments, but also current perpendicular to the planes of atoms geometries, consequences of tunneling, and finite nanostructures at or on metallic substrates. In order to give a more complete view of available ab initio methods also a non-relativistic approach based on the Tight Binding Linear Combination of muffin tin orbitals (TB-LMTO-) method and the so-called Kubo–Landauer equation in terms of transmission and reflection matrices is presented. A compilation of references with respect to ab-initio type approaches not explicitly discussed in here finally concludes the discussion of electric properties in solid systems with reduced dimensions.

Multilayer systems and symmetry

In this paper, concepts such as lattices and translational and rotational invariance are critically reviewed as far as their applications for infinite and semi-infinite multilayer systems are concerned. It turns out that new terms such as parent three-dimensional lattices and colloquial lattices have to be defined. Particular attention is given to the consequences of these new concepts as well as to a spin-polarized, fully relativistic description for magnetic multilayers within the local density functional approximation.

Noble metal capping effects on the spin-reorientation transitions of Co/Ru(0001)

Thin films of Co/Ru(0001) are known to exhibit an unusual spin reorientation transition (SRT) coupled to the completion of Co atomic layers for Co thicknesses under four layers. By means of spin-polarized low-energy electron microscopy, we follow in real space the magnetization orientation during the growth of atomically thick capping layers on Co/Ru(0001). Capping with noble metal (Cu, Ag and Au) elements modifies the SRT depending on the Co and overlayer thickness and on the overlayer material, resulting in an expanded range of structures with high perpendicular magnetic anisotropy. The origin of the SRT can be explained in terms of ab initio calculations of the layer-resolved contributions to the magnetic anisotropy energy. Besides the changes in the SRT introduced by the capping, a quantitative enhancement of the magnetic anisotropy is identified. A detailed analysis of the interplay between strain and purely electronic effects allows us to identify the conditions that lead to a high perpendicular magnetic anisotropy in thin hcp Co films.