A. P. Menushenkov

A Transition from Localized to Strongly Correlated Electron Behavior and Mixed Valence Driven by Physical or Chemical Pressure in ACo2As2 (A = Eu and Ca)

We demonstrate that the action of physical pressure, chemical compression, or aliovalent substitution in ACo2As2 (A = Eu and Ca) has a general consequence of causing these antiferromagnetic materials to become ferromagnets. In all cases, the mixed valence triggered at the electropositive A site results in the increase of the Co 3d density of states at the Fermi level. Remarkably, the dramatic alteration of magnetic behavior results from the very minor (<0.15 electron) change in the population of the 3d orbitals. The mixed valence state of Eu observed in the high-pressure (HP) form of EuCo2As2 exhibits a remarkable stability, achieving the average oxidation state of +2.25 at 12.6 GPa. In the case of CaCo2As2, substituting even 10% of Eu or La into the Ca site causes ferromagnetic ordering of Co moments. Similar to HP-EuCo2As2, the itinerant 3d ferromagnetism emerges from electronic doping into the Co layer because of chemical compression of Eu sites in Ca0.9Eu0.1Co1.91As2 or direct electron doping in Ca0.85La0.15Co1.89As2. The results reported herein demonstrate the general possibility of amplifying minor localized electronic effects to achieve major changes in materials properties via involvement of strongly correlated electrons.

Formation of Nanocrystalline Structures in the Ln 2 O 3 -MO 2 Systems (Ln = Gd, Dy; M = Zr, Hf)

The formation of (Ln3+)2(M4+)2O7 (Ln = Gd, Dy; M = Zr, Hf) nanocrystallites obtained by annealing mixed hydroxides LnM(OH)7 · nH2O (precursors) synthesized by coprecipitation has been studied by synchronous thermal analysis, X-ray diffraction (normal and anomalous diffraction of synchrotron radiation), and EXAFS. In the systems under consideration, heat treatment of the X-ray amorphous precursors leads to their dehydration, and at 600–700°C, nanocrystallites with an fcc structure of disordered fluorite start forming. A further increase in temperature is accompanied by crystallite growth (CDD) and considerable change in the local structure of the heat-treated compounds. The crystallization enthalpies and activation energies have been determined.

Study of Two-Way Shape Memory Behavior of Amorphous-Crystalline TiNiCu Melt-Spun Ribbons

Recently we reported on the development of a composite material exhibiting reversible shape memory effect. A Ti–25Ni–25Cu (at.%) alloy was obtained by the melt spinning technique as amorphous–crystalline ribbons with a thickness of approximately 40 μm. The thickness of the amorphous and crystalline layers (dа and dc, respectively) was varied by electrochemical polishing. It has been ascertained that with varying the relationship dc/dа the martensite transformation and shape-recovery temperatures do not actually change, while the minimum radius of the ribbon bending decreases from 8.0 mm to 2.4 mm with increasing the relationship dc/dа from 0.33 to 1.40. The maximum reversible strain comprises 0.4% at dc/dа = 0.82. On the basis of experimental data obtained the phenomenological description, providing an explanation for nature of the phenomena taking place in the rapidly quenched amorphous-crystalline ribbon composite, has been proposed.

A study of the formation of Ln2 + xMe2 − xO7 − x/2 (Ln = Gd, Dy; Me = Zr, Hf) nanocrystals

It has been established that the process of producing the Ln2 + xMe2 − xO7 − x/2 (Ln = Gd, Dy; Me = Zr, Hf) nanocrystals by calcination of hydroxides, which, in turn, have been produced by coprecipitation of metal salts, includes several stages. At the beginning, the X-ray amorphous structure of the precursors remains unchanged during dehydration; during subsequent heating to 600–700°C, nanocrystals with a disordered fluorite structure begin to be formed. An increase in the temperature above 700°C leads to an increase in the size of crystallites (coherent scattering regions). This process is accompanied by changes occurring in their local structure. In the nanocrystalline powders of Cd2Hf2O7 and Gd2Zr2O7 synthesized at 1200°C (6 h), the pyrochlore-type superstructure with the lattice parameters doubled relative to fluorite has been revealed. It has also been found that, possibly, the Dy2HfO5 sample at 1600°C (3 h) has a modulated structure.

Spin dynamics of the intermediate-valence compound EuCu2Si2

The dynamic magnetic response of the intermediate-valence compound EuCu2Si2 has been studied using inelastic neutron scattering. At low temperatures, strong renormalization of the 7F0 → 7F1 spin-orbit transition energy is detected; it is likely to be related to partial delocalization of the f electrons of Eu. An increase in the temperature increases the valence instability of europium and results in further changes in the magnetic excitation spectrum parameters and the appearance of an intense quasi-elastic component.

Features of the local structure of rare-earth dodecaborides RB12 (R = Ho, Er, Tm, Yb, Lu)

The parameters of the local crystal structure of dodecaborides RB12 (R = Ho, Er, Tm, Yb, Lu) have been determined by extended X-ray absorption fine structure (EXAFS) spectroscopy. It has been shown that the vibrations of the rare-earth ion with respect to the boron cage are well described in the harmonic approximation. At the same time, the displacement of rare-earth ions from equilibrium positions of the crystal structure should be taken into account to determine the length of the R-B bond. The analysis of EXAFS spectra has revealed the displacement of 1–6% of rare-earth ions by about 0.2–0.3 Å in all compounds under investigation; this displacement at low temperatures results in the formation of a cage glass phase.

Ce valence in intermetallic compounds by means of XANES spectroscopy

Abstract The cerium effective valence was investigated by means of CeL3-XANES spectroscopy in some intermediate valence Ce-based systems with different magnetic ordering mechanisms: CeNi doped with Nd, Pr and Gd in the temperature range 5–300 K, and Ce3Fe17–xMnx intermetallics. The dependences obtained are considered within the frames of generally accepted mechanisms of rare-earth ions intermediate valence states. Possible correlations between the cerium effective valence and the magnetic properties of compounds are also noted.

Correlation of magnetic properties with the local features of the electronic and crystal structure in the Ce2Fe17 − xMnx intermetallide: XAFS data analysis

The rearrangement of the local environment of cerium has been examined using extended X-ray absorption fine structure spectroscopy above the K-Ce absorption edge for various manganese contents and temperatures in Ce2Fe17 − xMnx intermetallics (x = 0, 1, 2). The valence state of cerium has been studied simultaneously by X-ray absorption near-edge structure spectroscopy above the L3-Ce absorption under the same conditions. A correlation has been revealed between the changes observed in the local electronic and crystal structure of Ce2Fe17 − xMnx compounds and the types of magnetic states in them.

Direct reconstruction of the two-dimensional pair distribution function in partially ordered systems with angular correlations

An x-ray scattering approach to determine the two-dimensional (2D) pair distribution function (PDF) in partially ordered 2D systems is proposed. We derive relations between the structure factor and PDF that enable quantitative studies of positional and bond-orientational (BO) order in real space. We apply this approach in the x-ray study of a liquid crystal (LC) film undergoing the smectic-A-hexatic-B phase transition, to analyze the interplay between the positional and BO order during the temperature evolution of the LC film. We analyze the positional correlation length in different directions in real space.

Spatially resolved x-ray studies of liquid crystals with strongly developed bond-orientational order.

We present an x-ray study of freely suspended hexatic films of the liquid crystal 3(10)OBC. Our results reveal spatial inhomogeneities of the bond-orientational (BO) order in the vicinity of the hexatic-smectic phase transition and the formation of large-scale hexatic domains at lower temperatures. Deep in the hexatic phase up to 25 successive sixfold BO order parameters have been directly determined by means of angular x-ray cross-correlation analysis (XCCA). Such strongly developed hexatic order allowed us to determine higher order correction terms in the scaling relation predicted by the multicritical scaling theory over a full temperature range of the hexatic phase existence.