Complex Magnetism of Lanthanide Intermetallics and the Role of their Valence Electrons: Ab Initio Theory and Experiment.

We explain a profound complexity of magnetic interactions of some technologically relevant gadolinium intermetallics using an ab initio electronic structure theory which includes disordered local moments and strong f-electron correlations. The theory correctly finds GdZn and GdCd to be simple ferromagnets and predicts a remarkably large increase of Curie temperature with a pressure of +1.5 K kbar(-1) for GdCd confirmed by our experimental measurements of +1.6 K kbar(-1). Moreover, we find the origin of a ferromagnetic-antiferromagnetic competition in GdMg manifested by noncollinear, canted magnetic order at low temperatures. Replacing 35% of the Mg atoms with Zn removes this transition, in excellent agreement with long-standing experimental data.

Atomic-scale engineering of magnetic anisotropy of nanostructures through interfaces and interlines.

The central goals of nanoscale magnetic materials science are the self-assembly of the smallest structure exhibiting ferromagnetic hysteresis at room temperature, and the assembly of these structures into the highest density patterns. The focus has been on chemically ordered alloys combining magnetic 3d elements with polarizable 5d elements having high spin-orbit coupling and thus yielding the desired large magneto-crystalline anisotropy. The chemical synthesis of nanoparticles of these alloys yields disordered phases requiring annealing to transform them to the high-anisotropy L1(0) structure. Despite considerable efforts, so far only part of the nanoparticles can be transformed without coalescence. Here we present an alternative approach to homogeneous alloys, namely the creation of nanostructures with atomically sharp bimetallic interfaces and interlines. They exhibit unexpectedly high magnetization reversal energy with values and directions of the easy magnetization axes strongly depending on chemistry and texture. We find significant deviations from the expected behaviour for commonly used element combinations. Ab-initio calculations reproduce these results and unravel their origin.

Magnetic ordering in Fe/Co sandwiches on Cu(100).

We investigate magnetic correlations and local magnetic moments at finite temperatures of some Fe and Co multilayers on Cu(100) substrates, such as Co(m)Fe(n)Co(m)/Cu(100) and Fe(m)Co(n)Fe(m)/Cu(100). We use an ab initio mean-field theory of magnetic fluctuations for layered materials based on the first-principles local spin-density functional theory implemented through the screened Korringa-Kohn-Rostoker method. We find that the presence of Fe layers in the neighbourhood of a Co layer always leads to a reduction in the magnetic moment of the Co atoms, whereas that of the Fe atoms is enhanced. Of particular interest is the lack of local moment formation on the single fcc-Co layer sandwiched between two fcc-Fe layers. However, a Co layer completely immersed in a Cu environment remains ferromagnetic. The Curie temperature of the Co(m)Fe(n)Co(m)/Cu(100) system oscillates as the Fe layer thickness is increased whereas that of the Fe(m)Co(n)Fe(m)/Cu(100) system increases almost monotonically with Co layer thickness.

Lanthanide contraction and magnetism in the heavy rare earth elements.

The heavy rare earth elements crystallize into hexagonally close packed (h.c.p.) structures and share a common outer electronic configuration, differing only in the number of 4f electrons they have. These chemically inert 4f electrons set up localized magnetic moments, which are coupled via an indirect exchange interaction involving the conduction electrons. This leads to the formation of a wide variety of magnetic structures, the periodicities of which are often incommensurate with the underlying crystal lattice. Such incommensurate ordering is associated with a 'webbed' topology of the momentum space surface separating the occupied and unoccupied electron states (the Fermi surface). The shape of this surface-and hence the magnetic structure-for the heavy rare earth elements is known to depend on the ratio of the interplanar spacing c and the interatomic, intraplanar spacing a of the h.c.p. lattice. A theoretical understanding of this problem is, however, far from complete. Here, using gadolinium as a prototype for all the heavy rare earth elements, we generate a unified magnetic phase diagram, which unequivocally links the magnetic structures of the heavy rare earths to their lattice parameters. In addition to verifying the importance of the c/a ratio, we find that the atomic unit cell volume plays a separate, distinct role in determining the magnetic properties: we show that the trend from ferromagnetism to incommensurate ordering as atomic number increases is connected to the concomitant decrease in unit cell volume. This volume decrease occurs because of the so-called lanthanide contraction, where the addition of electrons to the poorly shielding 4f orbitals leads to an increase in effective nuclear charge and, correspondingly, a decrease in ionic radii.

Mn-stabilized zirconia: from imitation diamonds to a new potential high-Tc ferromagnetic spintronics material.

From the basis of ab initio electronic structure calculations which include the effects of thermally excited magnetic fluctuations, we predict Mn-stabilized cubic zirconia to be ferromagnetic above 500 K. We find this material, which is well known both as an imitation diamond and as a catalyst, to be half-metallic with the majority and minority spin Mn impurity states lying in zirconia's wide gap. The Mn concentration can exceed 40%. The high-Tc ferromagnetism is robust to oxygen vacancy defects and to how the Mn impurities are distributed on the Zr fcc sublattice. We propose this ceramic as a promising future spintronics material.

Effect of pressure on magnetoelastic coupling in 3d metal alloys studied with x-ray absorption spectroscopy.

Using x-ray absorption spectroscopy, we have studied the effect of pressure on femtometer-scale bond strain due to anisotropic magnetostriction in a thin FeCo film. At 7 GPa local magnetostrictive strain is found to be larger than at ambient, in agreement with spin-polarized ab initio electronic structure calculations, but contrary to the expected effect of compression on bond stiffness. The availability of high pressure data on local magnetostrictive strain opens new capabilities for validating theoretical predictions and can lead to the development of materials with the desired properties.

Temperature dependent magnetic anisotropy in metallic magnets from an ab initio electronic structure theory: L1(0)-ordered FePt.

Using a first-principles, relativistic electronic structure theory of finite temperature metallic magnetism, we investigate the variation of magnetic anisotropy K with magnetization M in metallic ferromagnets. We apply the theory to the high uniaxial K material, L1(0)-ordered FePt, and find its magnetic easy axis perpendicular to the Fe/Pt layers for all M and K to be proportional to M2 for a broad range of values of M. For small M, near the Curie temperature, the calculations pick out the easy axis for the onset of magnetic order. Our ab initio results for this important magnetic material agree well with recent experimental measurements, whereas the single-ion anisotropy model fails to give the correct qualitative behavior.

Density functional study of the phase diagram and pressure-induced superconductivity in p: implication for spintronics.

The high-pressure phase diagram of P is studied using density functional total energy, linear response lattice dynamics and model Debye-Grüneisen theories. The volume dependent electron-phonon coupling lambda approximately 0.7-0.9 is extracted for the bcc structure and found to increase with increasing volume. We propose that this phase might be realized in epitaxial thin films using templates such as V(100), Fe(100), or Cr(100) relevant to spintronics applications.

Onset of magnetic order in fcc-Fe films on Cu(100).

On the basis of an ab initio theory of metallic magnetism in layered materials, we investigate the onset of magnetic order in thin (2-8 layers) fcc-Fe films on and embedded in Cu(100) substrates. In particular, we find an oscillatory dependence of the Curie temperatures on embedding depth, in excellent agreement with experimental data. The thermally induced spin fluctuations are treated within a mean-field disordered local moment picture and give rise to layer-dependent "local exchange splittings" in the electronic structure even in the paramagnetic phase. These features determine the magnetic intralayer and interlayer interactions which are strongly influenced by the presence and extent of the Cu cap.