Diffusion and solubility of helium in lead fluoride single crystals in the superionic transition region

Temperature curves of the diffusion coefficients and solubilities of helium in pure and holmium-doped lead fluoride crystals are obtained in the superionic phase-transition range. Possible mechanisms of the interaction of helium with ions are discussed, along with mechanisms of the solubility and diffusion of helium in a crystal. Fiz. Tverd. Tela (St. Petersburg) 40, 759–760 (April 1998)     

The low-temperature solubility of helium in quartz

Technical Physics - The solubility of helium in α- and β-quartz single crystals, optical quartz crystals, and Pyrex glass has been studied by the method of thermal desorption of helium...     

Mass spectrometric investigation of the low-temperature dimethyl ether oxidation in an atmospheric pressure laminar flow reactor

Low-temperature combustion is a major strategy today to reduce both soot and NO_x emission. Kinetic reaction models for low-temperature combustion which are validated against a wide range of experimental data are necessary e.g. for control purposes or as a basis for subsequent model reduction.In this study, the low-temperature oxidation of dimethyl ether in a highly diluted gas mixture was investigated experimentally in an atmospheric laminar flow reactor. The respective gas composition was analyzed by a time-of-flight mass spectrometer. This technique allows detection of all species simultaneously within the investigated temperature regime. Stoichiometries of ? = 0.8, 1.0, and 1.2 were studied with high temperature resolution in the range of 400–1200 K, and quantitative species mole fraction profiles have been determined.This wide temperature range comprises the different kinetic regimes occurring during the DME oxidation, which have been clearly resolved. The distinct negative temperature coefficient (NTC) region of the system was observed and extensive speciation is available. Special attention is given to species only occurring in the low-temperature region including formic acid and methyl formate.     

Mass-spectroscopic study of the diffusion and solubility of helium in submicrocrystalline palladium

By the method of helium thermal desorption from submicrocrystalline palladium presaturated in the gaseous phase, the diffusion coefficient D _eff and solubility coefficient C _eff of helium are measured in the range P=0–3 MPa and T=293–508 K. The pressure dependence of C _eff flattens at high pressures. At low saturation pressures, the temperature dependences of the diffusion and solubility coefficients may be divided into (1) high-temperature (400–508 K) and (2) low-temperature (293–400 K) ranges described by the exponentials D _{1, 2}=D ₀exp (−E _{1, 2} ^D /kT) and C _{1, 2}=C ₀exp (−E _{1, 2} ^S /kT). The energies of diffusion activation are E ₂ ^D =0.0036±0.0015 eV and E ₁ ^D =0.33±0.03 eV, and the solution energies are E ₂ ^S =−0.025±0.008 eV and E ₁ ^S =0.086±0.008 eV in the low-and high-temperature ranges, respectively. Mechanisms behind the diffusion and solution of helium are discussed.     

Mass spectrometric investigation of anions formed upon free electron attachment to nucleobase molecules and clusters embedded in superfluid helium droplets

Here we report the first mass spectrometric study of negative ions formed via free electron attachment (EA) to nucleobases (NBs) embedded in helium clusters. Pure and mixed clusters of adenine and thymine have been formed by pickup of isolated NB molecules by cold helium droplets. In contrast to EA of isolated molecules in the gas phase we observe a long-lived parent anion NB- and, in addition, parent cluster ions NB-n up to size n=6. Moreover, we show that a low energy electron penetrating into a doped helium droplet causes efficient damage of the embedded nucleobases via resonant, site selective, dissociative electron attachment.     

Mass-spectrometric analysis of diffusion and solubility of helium in cerium-gadolinium ceramics with a submicrocrystalline structure

Diffusion and solubility of helium in Ce_0.8Gd_0.2O_{1.9 − δ} ceramics (δ = 0, 0.015) with a submicrocrystal structure are studied by thermodesorption of helium from preliminarily saturated (in the gas phase) crystals at temperatures of 613 and 673 K in the saturated pressure range 0–21 MPa. It is shown that, in this ceramics (δ = 0), the defect-trap diffusion mechanism operates. The main positions for dissolution are neutral anion vacancies formed as a result of thermal dissociation of impurity-vacancy complexes and saturated up to ∼1 × 10¹⁹ cm⁻³ at P = 6 MPa and T = 673 K. The dissociation energy of the complex and the energy of helium dissolution in the neutral anion vacancy are estimated at ∼2 eV and below −0.3 eV, respectively.     

Ionic conductivity and anion diffusion in single crystals of lead chloride

The ionic conductivity and self-diffusion of chlorine ions in undoped single crystals of zone-refined lead chloride have been measured over the temperature range 625–370K. These measurements suggest that the conductivity and self-diffusion are due to simple vacancy migration as confirmed by the observed correlation factor. The activation energy of formation of vacancies is found to be 1.55 eV and that for migration of an anion is 0.38 eV. In the extrinsic region, the two measurements show marked discrepancies which are explained by assuming the presence of oxygen impurity ions in the lattice, and the mechanisms for their contribution to the observed excess conductivity are discussed.     

Electronic structure of lead (II) fluoride and lead (II) chloride crystals

The method of complete neglect of differential overlap was used to calculate the electronic structure of α PbF₂, β PbF₂, and PbCl₂ crystals which form the basic matrices for the synthesis of new superionic conductors. It was shown that the electronic subsystem is fairly stable on transition from the high-symmetry β PbF₂ crystal to the low-symmetry α PbF₂. The electronic structure of the cotunnite crystal PbCl₂ was calculated for the first time. Fiz. Tverd. Tela (St. Petersburg) 40, 235–236 (February 1998)     

The holographic investigation of diffusion of azo-dye in liquid crystals host

The diffusion of azo-dye (DR-1) in a planar liquid crystals host (5CB) at various temperatures has been investigated by laser-induced holographic grating relaxation technique. The decay of the diffraction intensity provides information about the diffusion of photoexcited azo-dye molecules. The relaxation time constants can be derived from the time dependence of the diffraction intensity fitted by a single exponential function. Thus, the diffusion coefficients parallel and perpendicular to the director of liquid crystals at various temperatures can be obtained from the plots of the reciprocal of the relaxation time versus the square of the grating vector. From the analysis of the holographic grating relaxation, the diffusion is faster along the molecular director than for the perpendicular case, and the diffusion increases with rising temperature either parallel or perpendicular to the nematic director of liquid crystals. PACS 42.40.Eq; 42.40.Lx     

Nonclassical rotational inertia in helium crystals

It has been proposed that the observed nonclassical rotational inertia (NCRI) in solid helium results from the superflow of thin liquid films along interconnected grain boundaries within the sample. We have observed NCRI in large (4)He crystals grown at constant temperature and pressure, demonstrating that the superfluid grain boundary model cannot explain the phenomenon.     

Zeeman relaxation of CaF in low-temperature collisions with helium

The collision-induced Zeeman relaxation rate for collisions of CaF X2Sigma(v(')=0) with 3He is measured to be Gamma(Z)=(7.7+5.4/-2.5)x10(-15) cm(3)/s at 2 K. This rate is a direct measurement of the influence of spin-rotation coupling on Zeeman relaxation in the first rotational level of CaF. The relationship of this rate to known molecular constants is consistent with recent theory of cold molecular collisions and outlines the (2)Sigma molecules conducive to magnetic trapping.     

Atomistics of helium diffusion in copper and tungsten

Using previously determined interatomic potentials, the activation energy for migration of a single substitutional helium atom in copper and tungsten has been determined. The mechanism of migration involves the jump of the helium atom out of the vacancy concurrent with the jump of a host atom into that vacancy. The helium then occupies the vacant site created by the jumping host atom, resulting in a substitutional helium at a distance of √2 r ₀ (√3r ₀) from its original site in copper (tungsten). The rate-limiting step in the process is found to be the jump of the helium out of the vacancy, the activation energy for which is 2.15 eV in copper and 4.69 eV in tungsten.     

Positronium diffusion in crystals

The temperature dependence of the diffusion coefficient is analyzed for the two cases of localized and delocalized positronium in a crystal. The diffusion coefficient for the localized positronium is calculated from the Kubo formula, while that for the free positronium is calculated in the relaxation-time approximation. The temperature dependence of the tunneling diffusion coefficient for positronium is specified by analogy with impuritons in a quantum crystal.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 25–28, July, 1981.     

Equilibrium shape of rotating helium crystals

We have studied theoretically the effects of rotation on the equilibrium shape of the interface between superfluid and solid helium. Surface structures in the shape of hillocks and ridges appear in the presence of a vortex lattice in the superfluid. These structures are very sensitive to the orientation of the interface boundary with respect to the crystal planes when surface stiffness is very anisotropic, as occurs well below the roughening transition. We predict the appearance of ring shaped facets for fast rotation speeds. These effects should be observable by using optical techniques.     

Measurement of the electron-atom collision integral in low-temperature helium plasma

An expression is obtained for the electron-atom collision integral for axisymmetric low-temperature plasmas. The Legendre components of the collision integral are determined experimentally by the probe method. Comparison of the measured Legendre components with their theoretical values shows that, depending on the plasma conditions, the collisional regime or a regime of dominant collective interactions is established in the system. Zh. Tekh. Fiz. 67, 19–24 (April 1997)     

Nonstoichiometry and low-temperature magnetic properties of FeSi crystals

The results of experimental and theoretical studies of the low-temperature properties of FeSi crystals are presented. The specific features of the magnetic susceptibility are shown to be related to the superparamagnetic behavior of impurity clusters. The thermomagnetic hysteresis phenomena observed are explained using the model of exchange-coupled clusters.     

X-ray determination of thermal expansion of cadmium fluoride and lead fluoride

The lattice parameters of CdF₂ andβ-PbF₂ have been determined over the temperature range 300–670 K. The coefficient of expansion at room temperature is 21·3 × 10⁻⁶ K⁻¹ and 25·4 × 10⁻⁶ K⁻¹ for CdF₂ and PbF₂ respectively and it increases linearly with temperature over the range of temperature covered. The Grüneisen parameter decreases with temperature in both the crystals.     

Self-trapped excitons in low-symmetry fluoride crystals

Triplet self-trapped excitons have been detected in low-symmetry crystals of the fluorides BaFCl₄, BaFBr, and LaF₃. In BaFBr crystals two types of excitons, on-center and off-center (with a symmetric or displaced configuration). The slow initiation of exciton luminescence in BaFBr is associated with the barrier transition from an on-center to an off-center configuration. In LaF₃ crystals tunnelling population of the exciton state also appears in the initiation. In LaF₃ crystals excitons appear only in the luminescence and excitation spectra while in the absorption spectra the exciton transitions are concealed beneath band-to-band transitions. A. P. Vinogradov Institute of Geochemistry, Siberian Branch of the Russian Academy of Sciences. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 45–56, November, 1996.