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 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.     

Low-temperature helium defectoscopy and interaction of helium with ions of cerium gadolinium ceramics Ce<Subscript>0.8</Subscript>Gd<Subscript>0.2</Subscript>O<Subscript>1.9</Subscript> with a submicrocrystalline structure

The concentration of unbound neutral anion vacancies in cerium gadolinium ceramics Ce_0.8Gd_0.2O_1.9 with a submicrocrystalline structure has been determined using low-temperature helium defectoscopy at temperatures ranging from 613 to 773 K and at saturation pressures from 0.05 to 12 MPa. It has been found that the energy of dissociation of impurity-vacancy complexes is 1.1 ± 0.2 eV, and the energy of dissolution of helium in defects is −0.8 ± 0.2 eV. The obtained results have been compared both with the experimental data on the energy of interaction between helium and ions of the cerium gadolinium ceramics and with the results of the quantum-chemical calculations. It has been demonstrated that the anomalously low value of the energy of helium dissolution in the studied ceramic samples is determined by the chemical interaction of helium with the nearest environment of the cerium cations.     

Experimental determination of the rate constant for spin exchange in collisions of polarized metastable helium atoms with ground-state cesium atoms

The rate constant for spin exchange in a system consisting of a metastable helium atom and an alkali-metal atom is determined. An experiment on optical orientation of atoms established that the rate constant for spin exchange in a collision of a metastable 2³ S ₁ helium atom with a cesium atom in the 6² S _1/2 ground state equals (2.8±0.8)×10⁻⁹ cm³ s⁻¹. The rate constant for chemoionization of cesium atoms by metastable helium atoms was determined at the same time to be (1.0±0.3)×10⁹ cm³s⁻¹. Pis’ma Zh. éksp. Teor. Fiz. 66, No. 3, 145–148 (10 August 1997)     

Helium defectoscopy of cerium gadolinium ceramics Ce0.8Gd0.2O1.9 with a submicrocrystalline structure in the impurity disorder region

The concentration of impurity anion vacancies formed upon the dissociation of gadolinium-vacancy complexes has been determined using helium defectoscopy of the cerium gadolinium ceramics Ce_0.8Gd_0.2O_1.9 with a submicrocrystalline structure in the temperature range T = 740–1123 K and at saturation pressures ranging from 0.05 to 15 MPa. It has been found that the energy of dissociation of gadoliniumvacancy complexes is E _eff ^D = 0.26 ± 0.06 eV, and the energy of dissolution of helium in anion vacancies in the impurity disorder region is E ^P = ?0.31 ± 0.09 eV. The proposed mechanism of dissolution has been confirmed by the investigation of the electrical conductivity of the cerium gadolinium ceramics, as well as by the high-speed molecular dynamics simulation of the dissociation of gadolinium-vacancy complexes. It has been assumed that a decrease in the effective dissolution energy in comparison with the results of the previously performed low-temperature investigations is caused by the mutual repulsion of vacancies formed upon the dissociation of gadolinium-vacancy complexes in highly concentrated solutions of gadolinium in CeO₂ with increasing temperature.     

Spin exchange and chemi-ionization during collisions of polarized metastable helium atoms with ground-state cesium atoms

The kinetics of the optical orientation of atoms in a helium-cesium gas-discharge plasma are considered, and kinetic equations describing the optical orientation of atoms in the case of two simultaneously occurring processes, viz., an elastic process (spin exchange) and an inelastic process (chemi-ionization), are derived. The rate constants of these processes are determined experimentally: C _se=(2.8±0.8)×10⁻⁹ cm³s⁻¹, C _ci=(1.0±0.3)×10⁻⁹ cm³s⁻¹. Zh. Tekh. Fiz. 69, 36–40 (September 1999)     

Absolute cross sections of electron attachment to molecular clusters. Part II: Formation of (H2O) N? , (N2O) N? , and (N2) N?

Absolute cross sections σ⁻(E, N) of electron attachment to clusters (H₂O) _N , (N₂O) _N , and (N₂) _N for varying electron energy E and cluster size N are measured by using crossed electron and cluster beams in a vacuum. Continua of σ⁻(E) are found that correlate well with the functions of electron impact excitation of molecules’ internal degrees of freedom. The electron is attached through its solvation in a cluster. In the formation of (H₂O) _N ⁻ , (N₂O) _N ⁻ , and (N₂) _N ⁻ , the curves σ⁻(N) have a well-defined threshold because of a rise in the electron thermalization and solvation probability with N. For (H₂O)₉₀₀, (N₂O)₃₅₀, and (N₂)₂₆₀ clusters at E = 0.2 eV, the energy losses by the slow electron in the cluster are estimated as 3.0 × 10⁷, 2.7 × 10⁷, and 6.0 × 10⁵ eV/m, respectively. It is found that the growth of σ⁻ with N is the fastest for (H₂O) _N and (N₂) _N clusters at E → 0 as a result of polarization capture of the s-electron. Specifically, at E = 0.1 eV and N = 260, σ⁻ = 3.0 × 10⁻¹³ cm² for H₂O clusters, 8.0 × 10⁻¹⁴ cm² for N₂O clusters, and 1.4 × 10⁻¹⁵ cm² for N₂ clusters; at E = 11 eV, σ⁻ = 9.0 × 10⁻¹⁶ cm² for (H₂O)₂₀₀ clusters, 2.4 × 10⁻¹⁴ cm² for (N₂O)₃₅₀ clusters, and 5.0 × 10⁻¹⁷ cm² for (N₂)₂₆₀ clusters; finally, at E = 30 eV, σ⁻ = 3.6 × 10⁻¹⁷ cm² for (N₂O)₁₀ clusters and 3.0 × 10⁻¹⁷ cm² for (N₂)₁₂₅ clusters. Original Russian Text ? A.A. Vostrikov, D.Yu. Dubov, 2006, published in Zhurnal Tekhnicheskoĭ Fiziki, 2006, Vol. 76, No. 12, pp. 1–15.     

Optical properties of the ternary compound Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Hg<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Se:Co

We present the results of experimental studies of the optical properties of cobalt-doped Cd _x H_1−x Se (x = 0.18) single crystals with cobalt ion concentrations of NCo = 5·10¹⁸, 5·10¹⁹, and 1·10²⁰ cm⁻³ at T = 90 K and 300 K. The composition (x = 0.18) of the Cd _x Hg_1−x Se solid solution was selected so that the hypothetical resonance level is found on the bottom of the conduction band. We show that the cobalt ions in the mercury selenide can form a resonance donor level only for cobalt concentrations N_Co < 5·10¹⁸ cm⁻³. For N_Co ∼ 5·10¹⁸ cm⁻³, the cobalt ions substitute for mercury atoms, forming a solid solution and leading to an increase in the bandgap width and a change in the physical properties. The solubility of cobalt in the HgSe lattice can be greater than 5%–10%. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 73–77, January–February, 2007.     

Propagation of nonequilibrium phonons in ferroelectric ceramics and single crystals

Phonon transport in ferroelectric ceramics and single crystals has been experimentally investigated. Our measurements indicate that, in the temperature range 1.7–3.8 K studied, the effective phonon diffusion coefficient behaves as D _eff∞T ⁻⁵ in ferroelectrics with a broadened phase transition. This experimental dependence is in accord with the presence of a plateau in the thermal conductivity of such materials. The scattering by domain walls in BaTiO₃ single crystals has been identified, and our results are in quantitative agreement with calculations. Zh. éksp. Teor. Fiz. 115, 624–631 (February 1999)     

Free carrier concentration and conductivity in chlorine doped lead telluride

Plasma resonance in the IR reflection spectra is used to measure the concentration and relaxation time of free charge carriers along with the conductivity in PbTe_{1 − x} Cl _x solid solutions. It is found that with increasing the chlorine concentration, the electron concentration and conductivity increase and reach saturation at x = 0.03 (n = 5.5 × 10¹⁹ cm⁻³, σ = 3750 Ohm⁻¹ · cm⁻¹). The relaxation time decreases with increasing the chlorine concentration and reaches the minimum value of 2.2 × 10⁻¹⁴ s at x = 0.03; then, it almost does not change.     

Formation of ordered helium pores in amorphous silicon subjected to low-energy helium ion irradiation

Thin transparent (for transmission electron microscopy, TEM) self-supported Si(001) films are irradiated on the (110) end face by low-energy (E=17 keV) He⁺ ions at doses ranging from 5×10¹⁶ to 4.5×10¹⁷ cm⁻² at room temperature. The TEM study of the irradiated Si films along the ion range shows that an a-Si layer forms in the most heavily damaged region and helium pores (bubbles) with a density of up to 3×10¹⁷ cm⁻³ and 2–5 nm in diameter nucleate and grow across the entire width of this layer. The growth of nanopores in the a-Si layer is accompanied by their linear ordering into chains oriented along the ion tracks. The absence of pores in the region that remains crystalline and has the maximal concentration of implanted helium is explained by the desorption of helium atoms from the thin film during the irradiation. After annealing at 600°C, the volume of immobile pores in the remaining a-Si layer increases owing to the capture of helium atoms from the amorphous matrix. Solid solution is shown to be the prevalent state of the helium implanted into the amorphous silicon. Linear features with a diameter close to 1 nm and density of about 10⁷ cm⁻¹ discovered in the helium-doped a-Si layer are identified as low-energy He⁺ ion tracks.     

Comparative Raman study of the Ti complex Cp2Ti(η2-C60) · C6H5CH3 and TixC60 films

Raman spectra from the first Ti fullerene complex Cp ₂Ti(η²-C₆₀) · C₆H₅CH₃ are presented. Compared to spectra of pure C₆₀, the spectra of the Ti complex exhibit a number of new peaks due to the symmetry lowering for C₆₀. The A _g(2) mode is downshifted by 12 cm⁻¹ compared to C₆₀, which corresponds to a charge transfer of one electron per Ti-C₆₀ bond. This value (6 cm⁻¹ for one transferred electron) is identical to the downshift of the A _g(2) mode in alkali metal fullerides with ionic bonding. The spectra of Cp ₂Ti(η²-C₆₀) · C₆H₅CH₃ were compared to the spectra of evaporated Ti_xC₆₀ films. The A _g(2) mode in Ti₄C₆₀ showed a downshift of about 25 cm⁻¹ compared to pure C₆₀, which corresponds to a charge transfer of one electron per Ti atom; this is similar to the ionic alkali metal fullerides and different from η²-C₆₀-type bonding. From Fizika Tverdogo Tela, Vol. 44, No. 3, 2002, pp. 483–485. Original English Text Copyright ? 2002 by Talyzin, Jansson, Usatov, Burlakov, Shur, Novikov. This article was submitted by the authors in English.     

The synthesis of boron-containing nanoparticles inert at room temperature

Boron-containing (C₂B₄H₂) _n nanoparticles with size 6.7, 7.8, and 10.8 nm inert at room temperature were synthesized. The synthesis was performed by the pyrolysis of gaseous carborane C₂B₄H₆ at 1200–1280 K and the initial carborane pressure (5–25) × 10⁻³ MPa. An analytic dependence relating the size of nanoparticles to the temperature and initial carborane pressure was obtained.     

Survey of the Star-Formation Regions Associated with Infrared Sources Observed in the <Emphasis Type="Italic">J</Emphasis> = 1−0 Line of the CO Molecule and Its Isotopes. Results of Observations Performed in the C<Superscript>18</Superscript>O(J = 1−0) Line

We present results of observations of 23 compact cores of molecular clouds associated with IRAS “ cold” infrared sources. The observations were performed in the J = 1−0 line of the C¹⁸O molecule on a 13.7-meter radio telescope of the Purple Mountain Observatory, China. The C¹⁸O (J = 1−0) line was detected in the emission of 21 objects. Column densities of the C¹⁸O and H₂ molecules towards the maximum of integral intensity of the C¹⁸O emission were estimated in the approximation of local thermodynamic equilibrium and amounted to (2.5–10.4) · 10¹⁵cm⁻² and (1.5–6.1) · 10²² cm⁻², respectively. The kinetic temperatures determined for these maxima from the CO lines vary from 14 to 45 K. For six objects, whose mapping has been almost completed, the dimensions of the C¹⁸O emission regions are estimated to range from 0.5 to 1.2 pc. The masses of these objects lie in the range of (390–1750) M_⊙ and are close to the estimates following from the virial theorem. The range of average densities of the objects is (0.3–1.4) · 10⁴ cm⁻³. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 48, No. 7, pp. 553–562, July 2005.     

Laser Raman and infra-red spectra of biomolecule: 5-aminouracil

Laser Raman (200–4000 cm⁻¹) and IR (200–4000 cm⁻¹) spectra of 5-aminouracil were recorded in the region 200–4000 cm⁻¹. Assuming a planar geometry and C_s point group symmetry, it has been possible to assign all the 36 (25a′ + 11a″) normal modes of vibration for the first time. The two NH bonds of the NH₂ group appear to be equivalent as the NH₂ stretching frequencies satisfy the empirical relation proposed for the two equivalent NH bonds of the NH₂ group. The two NH₂ stretching frequencies are distinctly separated from the CH/NH ring stretching frequencies. A strong and sharp IR band at 3360 cm⁻¹ could be identified as the anti-symmetric NH₂ mode whereas the band at 3290 cm⁻¹ with smaller density could be identified as the symmetric NH₂ stretching mode. All other bands have also been assigned different fundamentals/overtones/combinations.      

Evidence for formation of Se molecular clusters during precipitation of CdSe<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>S<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> nanoparticles in glass

While studying the effect of thermal treatment at 625–700°C on the formation of borosilicate glass-embedded CdSe or CdSe_1−x S _x nanocrystals, pronounced bands at 323 and 646 cm⁻¹ were observed in the Raman spectra. They are assigned to Se₂ clusters on the base of their frequency positions, widths, intensities, and resonance behavior. The precipitation of Se₂ molecular clusters in borosilicate glass is shown to occur when the heat treatment temperature and/or duration are beyond the range, most suitable for the formation of CdSe or CdSe-rich CdSe_1−x S _x nanocrystals.     

Crystallization-water-stimulated dynamic conductivity

In water-molecule-doped barium peroxide and barium oxide, a step increase in the dynamic conductivity to ∼10⁻³ Ω⁻¹ cm⁻¹ was found. The increase is observed when water molecules are present in two nonequivalent states in the lattice, with concentrations of the molecules n _t of ≥2.2×10²¹ cm⁻³. At n>n _t , the conductivity does not depend on the number of molecules in the lattice but is temperature-dependent, obeying the law σ(T = C ₁exp(−E ₁/kT) + C ₂exp(−E ₂/kT. The run of the σ(n, T) curve is explained by trapping electrons that result from H₂O dissociation and by two sorts of carrier jumps between localized and delocalized states.     

Measurement of the spin-exchange and chemical ionization rate constants in collisions of polarized metastable 23 S 1 helium atoms with 32 S 1/2 sodium atoms

Experimental data on the spin-exchange rate constants for the He(2³ S ₁)-Na(3² S _1/2) system are reported for the first time. Measurements show that the spin-exchange rate constant is C _se = (23 ± 11) × 10⁻¹⁰ cm³ s⁻¹ and the chemical ionization rate constant is C _si = (29 ± 14) × 10⁻¹⁰ cm³ s⁻¹ at a temperature of 420 K. The results are compared with the data calculated from the rate constants.     

Measurement of atomic parameters for the3 D 1 state of I–II

The decay rates of the³ D ₁ level of I–II and the 3s ₂ level of neon have been measured by the magnetic-field power dip method. The decay rate at the zero-pressure limit is found to be 7.1 MHz/2π for the³ D ₁ level. The collision cross-section for excited I ions with helium atoms equals 0.19×10⁻¹⁵ cm². This work was supported by project MR-1.5-1.05.     

Fabrication of a nanoparticle TiO<Subscript>2</Subscript> photoelectrochemical cell utilizing a solid polymeric electrolyte of PAN–PC–LiClO<Subscript>4</Subscript>

A nanoparticle TiO₂ solid-state photoelectrochemical cell utilizing as a solid electrolyte of poly(acrylonitrile)–propylene–carbonate–lithium perchlorate (PAN–PC–LiClO₄) has been fabricated. The performance of the device has been tested in the dark and under illumination of 100-mW cm⁻² light. A nanoparticle TiO₂ film was deposited onto indium tin oxide-covered glass substrate by controlled hydrolysis technique assisted with spin-coating technique. The average grain size for the TiO₂ film is 76 nm. LiClO₄ salt was used as a redox couple. The room temperature conductivity of the electrolyte is 4.2 × 10⁻⁴ S cm⁻¹. A graphite electrode was prepared onto a glass slide by electron beam evaporation technique. The device shows the rectification property in the dark and shows the photovoltaic effect under illumination. The best J _sc and V _oc of the device were 2.82 μA cm⁻² and V _oc of 0.58 V, respectively, obtained at the conductivity of 4.2 × 10⁻⁴ S cm⁻¹ and intensity of 100 mW cm⁻². The J _sc was improved by about three times by introducing nanoparticle TiO₂ and by using a solid electrolyte of PAN–PC–LiClO₄ replacing PVC–PC–LiClO₄ in the device. The current transport mechanism of the cell is also presented in this paper.