EPR spectroscopy and polarography of nitroazoles. 3. Nitropyrazoles

The results of an EPR investigation are presented with polarographs of electrochemical excitation of nitropyrazoles in acetonitrile. It is shown that 3- and 4-nitropyrazoles are excited in two single-electron stages with formation of dianion radicals. Upon excitation, N-alkylnitropyrazoles form stable anion radicals. 1-Nitro- and 1,4-dinitropyrazoles are excited upon splitting off of the NO₂ anion. Excitation potentials of the nitropyrazoles and hyperfine interaction constants for the corresponding ion radicals are given.See [1] for Communication 2.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 523–527, April, 1982.     

Mössbauer study of carbide phases in catalysts for ammonia synthesis

Samples of a catalyst CA-1 for ammonia synthesis were studied. After reduction the samples were treated with CO₂ or with a mixture of 1% O₂+2.4% H₂O+CO₂ at temperatures between 600 and 783 K. Mössbauer spectroscopy data indicate that above 600 K carbide phases and magnetite are formed. A probable mechanism for carbide formation is suggested.     

Influence of unstable valence of cerium ions on the crystal field in ReNi compounds

To examine the effect of hybridization of 4f electrons with conduction electrons on the crystal field potential using neutron spectroscopy, we studied the effects of the crystal electric field (CEF) in intermetallic compounds of the type ReNi, in which chemical substitution is followed by a transition of the cerium ions from an intermediate valence state to the Kondo state. Measurements were performed both on cerium ions in the compounds Ce_1−x La_xNi (x=0.5, 0.8), where they have a whole-number population of the 4f shell, and on the paramagnetic impurity ion Nd in the series of compounds Re_1−x Nd_xNi (Re=Ce, La, Y), in which the cerium ions are found either in an intermediate valence state or in the Kondo state. From the neutron inelastic magnetic scattering spectra on Nd ions, we have reconstructed the crystal field parameters in ReNi compounds and calculated the CEF level diagram of Ce ions in these compounds as functions of the interion distances Re-Ni. The results of our calculations are in good agreement with the experimentally determined splitting diagram of the ground-state multiplet of the Ce ions. We have determined that as the degree of hybridization with the conduction electrons grows the CEF potential varies considerably and the effective splitting of the 4f shell of the cerium ions increases. The estimated energy scale of the splitting of the ground-state multiplet of the Ce³⁺ ions in the ReNi CEF (Δ_CEF∼15 meV) turns out to be commensurate with the Kondo temperature (T _K ;140 K for CeNi. Analysis indicates that the CEF potential has a substantial effect on the formation of the valence-unstable ground state of the f shell in this compound. Zh. éksp. Teor. Fiz. 113, 1731–1747 (May 1998)     

Microscopic nature of the extremely high specific heat of rare earth intermetallic compounds at low temperatures and the possibility of its application in technical superconductivity

The presence of an unfilled f-electron shell in rare earth intermetallic compounds under conditions of strong electron correlation between localized and delocalized electrons is responsible for the formation of local magnetic moments. According to the data of neutron, synchrotron, and other investigations of a number of such systems, the interaction of these moments with the local crystalline environment, hybridization with conduction electrons, f-f correlations (i.e., both one-site and cooperative phenomena), and combinations of these main effects form the physical base for the reconstruction of the excitation spectrum of an f-electron system and appearance of pronounced specific features of thermodynamic characteristics. The range of characteristic temperatures of these anomalies is determined by the interaction energy, which generally corresponds to the range 1–100 K. For some intermetallic compounds, the additional component of the specific heat (of electron origin) may greatly (by two to three orders of magnitude) exceed the specific heat of conventional structural materials. This feature makes it possible to consider such systems as promising functional materials (a kind of thermodynamic dampers) capable of compensating for various thermal perturbations in low-temperature super-conducting magnetic systems.     

Increase in the superconducting transition temperature in Zr-Hf alloys due to <Emphasis Type="Italic">s-d</Emphasis> electron transfer under pressure

Correlation between the roughness of neighboring interfaces (roughness cross correlation) in a Ni/C X-ray multilayer mirror (XMM) prepared by laser ablation was studied by measuring X-ray diffuse scattering (XDS). The XDS intensities in the vicinity of the first Bragg reflection were measured at different photon energies: slightly below (8.325 keV) and slightly above (8.350 keV) the nickel photoabsorption K edge. The effective screening of the contribution from the deep layers to the XDS cross section due to the strong damping of the wave field at a photon energy higher than the photoabsorption edge allowed information on the character of the in-depth roughness cross correlation in the sample to be obtained. In particular, the characteristic lateral correlation length of the roughness was 0.35 µm at a photon energy of 8.325 keV (the contribution to the XDS cross section of the entire XMM volume), and it increased to 0.4 µm at a photon energy of 8.350 keV (predominantly the contribution from the upper layers). These data give direct evidence for the mechanism of smoothing of the interfacial roughness in the process of Ni/C XMM growth on anomalously large (up to micron) spatial scales. It was found that only rough large-scale defects with sizes of ≥10 µm are reproduced reasonably well from layer to layer. The processes of viscous flow and (or) reevaporation of high-energy target ions during deposition, which is characteristic of the laser method of XMM preparation, may serve as a possible explanation of the observed phenomenon.