Importance of spin-orbit effects on the isomerism profile of Au3: an ab initio study

Two-component relativistic density functional theory combined with high-level ab initio correlation techniques was applied to the study of the electronic structure and isomerism of Au(3). All calculations were performed with accurate small-core shape-consistent relativistic pseudopotentials. Density functional theory was used to determine the equilibrium structures of the Au(3) isomers and isomerization path and to estimate the contributions of spin-orbit effects to the ground state electronic energy along the path. The reliability of these estimates was verified through independent many-body multipartitioning perturbation theory calculations. Spin-orbit corrections were used to refine the isomerization energy profile computed by spin-orbit-free coupled cluster methods.     

Emission processes accompanying deformation and fracture of metals

Present-day physical methods of investigation reveal that the fracture and plastic deformation of metals is accompanied by emission processes, in particular, by luminescence and emission of electrons. All the metals studied thus far exhibit a capability of luminescence. The intensity, duration, and spectrum of mechanoluminescence are different for different metals. The intensity is determined by the mechanical and thermal characteristics. For a given metal, the intensity depends on dislocation density in the structure and the sample loading rate. The spectrum of noble metals is governed by the electronic structure of surface states. The dynamics of mechanoluminescence and electron emission (exoemission) depends on the rate of stress variation in the sample under study. This permits one to consider the mechanoluminescence and exoemission not only as physical characteristics but also as a potential tool for probing surface states in metals and the kinetics of emergence of mobile dislocations on the surface with a high time resolution. Fiz. Tverd. Tela (St. Petersburg) 41, 841–843 (May 1999)     

Transformations of the Burnett components of transport relations in gases

The well-known expressions for the Burnett components of the stress tensor and the heat flux vector in a monatomic gas are transformed to a more effective form. The greatest simplifications are obtained for the stress tensor when using the usually employed approximate values of the Burnett transport coefficients, which are exact for the gas consisting of Maxwellian molecules.     

Status of the Navier–Stokes Equations in Gas Dynamics. A Review

The existing ideas on the status of the Navier–Stokes equations are changed in taking into account the following facts: generally speaking, the terms of these equations neglected in the boundary layer equations are of the order of certain Burnett terms in the conservation equations; the Navier–Stokes equations cannot be used to describe slow nonisothermal gas flows since in this case it is necessary to take the Burnett temperature stresses into account; and in the transport relations the Burnett terms determine certain effects (for example, the mechanocaloric effect).     

Refinement of the crystal structures of biomimetic weddellites produced by microscopic fungus Aspergillus niger

The single-crystal structures of four biomimetic weddellites CaC₂O₄ · (2 + x)H₂O with different contents of zeolitic water (x = 0.10–0.24 formula units) produced by the microscopic fungus Aspergillus niger were refined from X-ray diffraction data (R = 0.029–0.038). The effect of zeolitic water content on the structural stability of weddellite was analyzed. The parameter a was shown to increase with increasing x due to the increase in the distance between water molecules along this direction. The water content and structural parameters of the synthesized weddellites are similar to those of weddellites from biofilms and kidney stones.     

The kinetics and mechanism of reactions of aliphatic stable nitroxyl radicals with alkyl and peroxide radicals during styrene oxidation

A kinetic study (EPR, microvolumometry), quantum-chemical analysis (DFT B3LYP/6-31G*), and kinetic simulation of the antioxidant activity of aliphatic stable nitroxyl radicals during styrene oxidation was performed. The key reactions constituting the detailed mechanism of the process were analyzed. It was shown that the inhibiting action of nitroxyl radicals was caused by their reaction not only with alkyl radicals but also with substrate peroxy radicals, which resulted in the regeneration of nitroxyl radicals in chain-termination steps.     

Hole defects in the crystal structure of synthetic lipscombite (Fe 4.7 3+ Fe 2.3 2+ )[PO4]4O2.7(OH)1.3 and genetic crystal chemistry of minerals of the lipscombite-barbosalite series

The crystal structure of a synthetic analog of the mineral lipscombite (Fe _2.3 ²⁺ Fe _4.7 ³⁺ )[PO₄]₄O_2.7(OH)_1.3 obtained under hydrothermal conditions in the LiF-Fe₂O₃-(NH₄)₂HPO₄-H₂O system is resolved (R = 0.040) by X-ray diffraction analysis (Bruker Smart diffractometer with a highly sensitive CCD detector, MoK _α radiation): a = 14.776(3) Å, b = 14.959(3) Å, c = 7.394(1) Å, β = 119.188(4)°, sp. gr. C2/c, Z = 4, ρ_exp = 3.8 g/cm³, ρ_calcd = 3.9 g/cm³. Fe²⁺ and Fe³⁺ cations are statistically distributed in each of four crystallographically independent positions, while occupying the corresponding octahedra with probabilities of 60, 90, 100, and 91%. The ratio Fe²⁺/Fe³⁺ in the composition of the crystals was established by Mössbauer spectroscopy. Lipscombite is interpreted as a mineral of variable composition described by the formula (Fe _x ²⁺ Fe _n?x ³⁺ )[PO₄]₄O_y(OH)_4?y . The field of stability is determined as a function of the iron content and the ratio Fe²⁺/Fe³⁺. It is shown that at n = 6 iron cations are ordered in octahedra and barbosalite structure is formed. An interpretation of genetically and structurally related members of the lipscombite family within a unified polysomatic series is proposed.     

The composition of combustion products formed from gasoline-hydrogen-air mixtures in a constant-volume spherical chamber

The experimental unit, procedure for testing, and the results and reliability of the determination of the composition of combustion products formed from gasoline-hydrogen-air (containing 0–100% hydrogen), gasoline-air, and isooctane-hydrogen-air mixtures in a constant-volume chamber are described. Studies were performed at initial mixture temperatures of 20–70°C and a 0.1 MPa pressure.     

Luminescence Monitoring of Lanthanide Catalysts for Diene Polymerization

Changes in the luminescence characteristics of Tb³⁺ and Ce³⁺ lanthanide ions in the interaction of LnCl₃ · 3(BuO)₃PO complexes with iso-Bu₃Al in the absence and presence of piperylene were studied. As a result, a new luminescence approach was proposed to study reaction mechanisms in the synthesis of lanthanide catalysts for diene polymerization.     

Synthesis and phase formation in M 0.5(1+x) 2+ FexTi2−x (PO4)3 phosphate series

New complex phosphates of titanium, iron, and alkaline-earth metals have been synthesized. X-ray powder diffraction, differential thermal analysis (DTA), and IR spectroscopy are used to study phase formation in the series of M_0.5(1+x)Fe_xTi_2?x (PO₄)₃ (M = Mg, Ca, Sr, Ba) phosphates. Individual compounds and solid solutions are found to crystallize in the NaZr₂(PO₄)₃ and K₂Mg₂(SO₄)₃ structure types. Their crystal parameters are calculated. CaFeTi(PO₄)₃ is studied using Mössbauer spectroscopy. Its structure is refined by the Rietveld method: space group $R\bar 3$ c, Z = 6, a = 8.5172(1), Å, c = 21.7739(4) Å, V = 1367.91(4) ų.