Accurate depolarization ratio measurements for all diatomic hydrogen isotopologues

The Raman depolarization ratios for individual Q₁(J”) branch lines of all diatomic hydrogen isotopologues – H₂, HD, D₂, HT, DT, and T₂ – were measured, for all rotational levels with population larger than 1/100 relative to the Boltzmann maximum at room temperature. For these measurements, the experimental setup normally used for the monitoring of the tritiated hydrogen molecules at KArlsruhe TRItium Neutrino experiment was adapted to optimally control the excitation laser power and polarization, and to precisely define the Raman light collection geometry. The measured Raman depolarization values were compared to theoretical values, which are linked to polarizability tensor quantities. For this, the ‘raw data’ were corrected taking into account distinct aspects affecting Raman depolarization data, including (1) excitation polarization impurities; (2) extended Raman excitation volumes; and (3) Raman light collection over finite solid angles. Our corrected depolarization ratios of the hydrogen isotopologues agree with the theoretical values (based on ab initio quantum calculations by R.J. LeRoy, University of Waterloo, Canada) to better than 5% for nearly all of the measured Q₁(J”) lines, with 1σ confidence level. The results demonstrate that reliable, accurate Raman depolarization ratios can be extracted from experimental measurements, which may be substantially distorted by excitation polarization impurities and by geometrical effects. Copyright © 2013 John Wiley & Sons, Ltd.     

Hydrogen diffusion constants in stainless steel and Pd60Ag40 alloy, and permeability of diaphragms made of these metals

Hydrogen permeability through diaphragms made of 12X18H12T stainless steel and Pd₆₀Ag₄₀ alloy under electrolytic hydrogen saturation has been studied with an electrolytic cell with a vacuum chamber. Hydrogen diffusion constants D _H = 3.86 × 10⁻¹⁰ cm² s⁻¹ for stainless steel and D _H = 4.36 × 10⁻⁸ cm² s⁻¹ for Pd₆₀Ag₄₀ alloy have been determined at a temperature of 40°C using the Berrer relations.     

Spin-spin interaction of Ni2+ ions in ZnSiF6·6H2O

The angular dependences of the electron spin resonance spectrum of 1% Ni²⁺ ions in a ZnSiF₆·6H₂O matrix are investigated experimentally at 36 GHz and 4.2 K. Besides the main spectrum of the isolated ion, we observed a spectrum due to interacting pairs of Ni²⁺ ions, located in the first (nn) and second (2n) coordination spheres and coupled by, besides the magnetic dipole-dipole interaction, isotropic exchange: J _nn = (−197±1)×10⁻⁴, J _2nα = (−5±1)×10⁻⁴, and J _2nβ = (3±2)×10⁻⁴ cm⁻¹. Lines due to other isolated Ni²⁺ ions, which have a different initial splitting D, are also present in the spectrum with intensity comparable to the pair spectrum. Low-symmetry distortions of the crystal field are observed, caused by a pair of impurity ions located close to one another. It is shown that the previously proposed interpretation is incorrect. Fiz. Tverd. Tela (St. Petersburg) 41, 1602–1608 (September 1999)     

Pyrophosphate Selective Recognition in Aqueous Solution Based on Fluorescence Enhancement of a New Aluminium Complex

A novel and simple fluorescence enhancement method for selective pyrophosphate(PPi) sensing was proposed based on a 1:1 metal complex formation between bis(8-hydroxy quinoline-5-solphonat) chloride aluminum(III) (Al(QS)₂Cl), (L) and PPi in aqueous solution. The linear response range covers a concentration range of 1.6 × 10⁻⁷ to 1.0 × 10⁻⁵ mol/L of PPi and the detection limit of 2.3 × 10⁻⁸ mol/L. The association constant of L-PPi complex was calculated 2.6 × 10⁵ L/mol. L was found to show selectively and sensitively fluorescence enhancement toward PPi over than I₃^-, NO₃^-, CN⁻, CO₃²⁻, Br⁻, Cl⁻, F⁻, H₂PO4⁻ and SO₄²⁻, which was attributed to higher stability of inorganic complex between pyrophosphate and L.     

Europium-sensitized Chemiluminescence of System Tetracycline–H<Subscript>2</Subscript>O<Subscript>2</Subscript>–Fe(II)/(III) and Its Application to the Determination of Tetracycline

Chemiluminescence (CL) of the reaction system tetracycline–H₂O₂–Fe(II)/(III)–Eu(III) was used for the determination of tetracycline hydrochloride in water, pharmaceutical preparations, and honey. The CL spectrum registered for this system shows emission bands typical of Eu(III) ions, with a maximum at λ ∼ 600 nm, corresponding to the electronic transitions of ⁵D₀ → ⁷F₁ and ⁵D₀ → ⁷F₂. A strong chemiluminescence intensity characteristic of europium(III) ions in the system tetracycline–H₂O₂–Fe(II)/(III)–Eu(III), as contrasted to the emission of the system tetracycline–H₂O₂–Fe(II)/(III) without Eu(III), proves that the Eu(III) ion plays the role of a chemiluminescence sensitizer, accompanying tetracycline oxidation in the Fenton system (H₂O₂–Fe(II)/(III)). A linear dependence was observed for the integrated CL light intensity on the tetracycline concentration in the range of 2 × 10⁻⁷ to 3 × 10⁻⁵ mol l⁻¹ with the detection limit of 5 × 10⁻⁸ mol l⁻¹ in aqueous solution.     

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.     

Raman spectrographic system for quantitative analysis of isotopic hydrogen mixtures for muon catalysis experiments

We show that Raman spectral lines from H₂, D₂, T₂, HD, HT and DT are readily resolved, permitting an effective means to analyze isotopic hydrogen mixtures used in muon-catalyzed fusion experiments. We propose a Raman spectrographic system to allow for real-time analysis of targets involving all three isotopes of hydrogen.     

Study of Enhanced Chemiluminescence of Diperiodatocuprate (III) on 1,10-Phenanthroline/Hydrogen Peroxide/Cetyltrimethylammonium Bromide System

In the paper, a chemiluminescence (CL) system was developed based on the catalytical effect of diperiodatocuprate (III) (DPC) on the 1,10-phenanthroline (phen)/hydrogen peroxide (H₂O₂) in the presence of cetyltrimethylammonium bromide (CTAB). The effects of experimental conditions were investigated. Meanwhile the increase of CL intensity of the DPC/phen/H₂O₂/CTAB system is proportional to the concentration of phen in the range of low concentration. The linear range of the calibration curve is 5.0 × 10⁻⁹–1.0 × 10⁻⁶ mol L⁻¹, and the corresponding detection limit is 1.9 × 10⁻⁹ mol L⁻¹. The effects of phenolic compounds (PCs) on the system were investigated. Hydroquinone was used as an example to investigate the application of the CL system to the determination of PCs. The quenched CL intensity is linearly related to the logarithm of concentration of hydroquinone. The linear range of the calibration curve is 2.5 × 10⁻⁹–1.0 × 10⁻⁵ g mL⁻¹, and the corresponding detection limit is 1.8 × 10⁻⁹ g mL⁻¹. This phen and hydroquinone can be synchronously determined. The method was applied to the determination of hydroquinone in water samples and the recoveries were from 92% to 106%.     

Non-steady-state photo-EMF in nanostructured GaN and polypyrrole within porous matrices

We report an experimental investigation of the non-steady-state photoelectromotive force in nanostructured GaN within porous glass and polypyrrole within chrysotile asbestos. The samples are illuminated by an oscillating interference pattern created by two coherent light beams and the alternating current is detected as a response of the material. Dependences of the signal amplitude versus temporal and spatial frequencies, light intensity, and temperature are studied for two wavelengths λ=442 and 532 nm. The conductivity of the GaN composite is measured: σ=(1.1–1.6)×10⁻¹⁰ Ω⁻¹ cm⁻¹ (λ=442 nm, I ₀=0.045–0.19 W/cm², T=293 K) and σ=(3.5–4.6)×10⁻¹⁰ Ω⁻¹ cm⁻¹ (λ=532 nm, I ₀=2.3 W/cm², T=249–388 K). The diffusion length of photocarriers in polypyrrole nanowires is also estimated: L _D=0.18 μm.     

Impurity effects on the critical behaviour of the electrical resistance of binary liquid mixtures

The electrical resistance of the binary liquid system cyclohexane + acetic anhydride is measured, in the critical region, both in the pure mixture and when the mixture is doped with small amounts (≈ 100 ppm) of H₂O/D₂O impurities.T _c was approached to aboutt=3×10⁻⁶ wheret=(T −T _c )/T _c . The critical exponentb ≈ 0.35 in the fit of the resistance data to the equationdR/dT ∼t ^−b does not seem to be affected appreciably by the impurities. There is a sign reversal ofdR/dt in the non-critical region. Binary liquid systems seem to violate the universality of the critical resistivity.     

Quantum and semiclassical oscillations in the organic metal (BEDO-TTF)2Clx(H2O)y

We study quantum (Shubnikov-de Haas and de Haas-van Alphen) oscillations and angular oscillations of the reluctance in the organic quasi-two-dimensional metal (BO)₂Cl_x(H₂O)_y. We show that the Fermi surface in this compound consists of a slightly corrugated cylinder with its axis perpendicular to the conducting plane. The cross section of the cylinder in this plane is a perfect circle of radius k _F≃3×10⁷ cm⁻¹. The effective carrier mass associated with this cylinder is m*=(1.65–2.0) m ₀ in the conducting plane, while the Dingle temperature is T _D=3–4 K. Zh. éksp. Teor. Fiz. 114, 1137–1146 (September 1998)     

Diffusion study of nitrogen implanted into <Emphasis Type="Italic">α</Emphasis>-Hf using the nuclear resonance technique

The diffusion of nitrogen in α-Hf was studied in the temperature range of (823–1123) K using the ion implantation and nuclear resonance techniques. The measurements show that the diffusion coefficients follow the Arrhenius behavior D(T)=D ₀exp (−Q/RT) with D ₀=(5.5±2.1)×10⁻⁷ m²/s and Q=(228±1) kJ/mol. A comparison of the present results with the previous one is done.     

Cross sections for rotational excitation in He－H2 collisions

Close coupling calculations have been carried out for rotational excitations in He－H₂ collisions with symmetric isotopic substitution (He－H₂, D₂, T₂) and asymmetric isotopic substitution (He－HD, HT, DT). Cross sections have been obtained at the incidence energy of 0.3eV. Based on the calculations, the effect of isotopic substitution on atom－diatom collisions is discussed.     

Probing the field-induced variation of the chemical potential in Bi2Sr2CaCu2Oy via magneto-thermopower measurements

Approximating the shape of the magneto-thermoelectric power (TEP) ΔS(T,H) measured in Bi₂Sr₂CaCu₂O_y by an asymmetric linear triangle of the form ΔS(T,H)≃S _p (H)±B ^±(H)(T _c −T) with positive B ⁻(H) and B ⁺(H) defined below and above T _c , we observe that B ⁺(H) ≃2B ⁻(H). To account for this asymmetry, we explicitly introduce the field-dependent chemical potential μ(H) of holes into the Ginzburg-Landau theory and calculate both an average ΔS _av(T,H) and fluctuation contribution ΔS _fl(T,H) to the total magneto-TEP ΔS(T,H). As a result, we find a rather simple relationship between the field-induced variation of the chemical potential in this material and the above-mentioned magneto-TEP data around T _c , viz. Δ μ(H)∝S _p (H). Zh. éksp. Teor. Fiz. 116, 257–262 (July 1999) Published in English in the original Russian journal. Reproduced here with stylistic changes by the Translation Editor.     

Kinetics of the formation of gas bubbles during polarization of copper and graphite electrodes in electrolytic aqueous solutions

The adsorption and kinetic processes of the formation of gas bubbles passivating the surface during polarization of copper and graphite electrodes in 1% aqueous solution of sulfuric acid have been investigated. Three stages of the process related to the recharging of the double electric layer—adsorption accumulation of the gas escaping from the surface, the critical nucleation of the gas bubbles, and their subsequent growth—have been revealed, distinguished, and quantitatively estimated. It has been shown that potential leveling at the steady-state value specified by the Tafel equation is unambiguously associated with achievement of the limiting surface area screened by the gas bubbles for each particular current density. The surface diffusion constants D _H = (1.5–4.4) × 10⁻⁴ and (0.1–3.8) × 10⁻⁵ cm²/s of hydrogen on copper and graphite, respectively, and D _O = (1.8–4.5) × 10⁻⁷ cm²/s of oxygen on graphite during the motion toward the drain (the gas bubbles) have been calculated.     

Weak exchange interactions in the heteronuclear crystal CuPr2(CCl3COO)8·6H2O

The new heteronuclear crystal CuPr₂(CCl₃COO)₈·6H₂O, constructed of chains containing copper and praseodymium atoms, has been synthesized and investigated by EPR at 9.3 GHz at temperatures ranging from room temperature down to 10 K. At temperatures T∼300–130 K, EPR spectra are observed which are characteristic of isolated polyhedra of copper ions with g _z=2.330±0.005, g _x,y =2.053±0.005, A _z=139×10⁻⁴ cm⁻¹, and A _x,y <26×10⁻⁴ cm⁻¹. At temperatures T<130 K a complex spectrum is observed, associated with the appearance of weak exchange interactions between the copper ions in the chain (J _Cu-CuΣS _i·S _i+1), comparable in magnitude with the hyperfine interactions J _Cu-Cu=0.015 cm⁻¹ at T=10 K. The magnitude of the exchange interaction decreases smoothly as the temperature is raised. It is conjectured that orbitals of the praseodymium ions participate in the process of indirect exchange between the copper ions. Fiz. Tverd. Tela (St. Petersburg) 41, 2154–2157 (December 1999)     

REMPI as a tool for studies of OH radicals in catalytic reactions

2 +? O₂→H₂O on polycrystalline Pt foils has been studied by detection of desorbing OH radicals using the Resonance Enhanced Multiphoton Ionization, REMPI, technique. The measurements were performed at catalyst temperatures of 1000–1400 K and a total pressure below 10^-4 mbar. The studies of OH desorption by REMPI were achieved using a two-photon excitation D²Σ^-–X²Π (1–0), followed by one-photon ionization. The ions were detected in a time-of-flight mass spectrometer, TOF-MS, in order to avoid interference from non-resonantly ionized molecules. By applying TOF-MS, a simultaneous non-resonant ionization and detection of H₂, O₂ and H₂O was achieved. Recorded REMPI spectra were compared with spectra simulated using known molecular constants. The kinetics of the reaction derived from the measurements were compared with what was obtained in earlier LIF detection of OH, performed at higher total reactant pressure using the A–X transition. REMPI TOF-MS is shown to be a complement to LIF for reaction studies below 5×10^-4 mbar total pressure, where LIF is too insensitive for quantification. The reaction kinetics was found to be in agreement with a theoretic model and previous LIF studies. Received: 8 March 1996/Revised version: 4 October 1996     

Influence of Ar, Ne, Xe, and CCl4 impurities on luminescence kinetics of Cd II ions (5s22D5/2-5p2P3/2 transition, λ = 441.6 nm) in He-Cd mixture

The luminescence kinetics of the Cd II ion at a wavelength of 441.6 nm has been studied experi-mentally in a high-pressure He-Cd mixture in the presence of Ar, Ne, Xe, and CCl₄ impurities. Cadmium ions were excited through the bombardment of a cadmium foil heated up to 240°C by a pulsed electron beam with an electron energy of 150 keV, a pulse duration of 3 ns, and a current of 500 A. The constants of collisional quenching of the Cd II 5s ^{2 2} D _5/2 level by Ar, Ne, and Xe atoms and CCl₄ molecules and the integral luminescence quenching constants of this level in the helium medium by these impurity gases have been determined. The constants of collisional quenching appeared to be 8.1 × 10⁻¹² (Ar), 1.2 × 10⁻¹² (Xe), 1.5 × 10⁻¹³ (Ne), and 1.8 × 10⁻¹⁰ cm³/s (CCl₄, for λ = 325 nm), while the integral constants were found to be, respectively, 4.1 × 10⁻¹¹, 3.4 × 10⁻¹¹, 9.5 × 10⁻¹², 1.4 × 10⁻⁹ cm³/s for Ar, Ne, Xe, and CCl₄ at a buffer gas pressure of 1 atm. Original Russian Text ? A.I. Miskevich, Liu Tao, 2009, published in Optika i Spektroskopiya, 2009, Vol. 107, No. 1, pp. 45–49.     

Heat capacity of MnBr2·4H2O near the antiferromagnetic transition temperature

Heat capacity of MnBr₂·4H₂O has been measured in the critical region around the Neel temperature. The data can be fitted, over a restricted range of |t|⩽10⁻², to the asymptotic power law. The critical exponents and the amplitudesA andA′ are not consistent with any theoretic predictions. However when scaling constraints are imposed, their values agree with the parameters of Ising model. Corrections to scaling are necessary to extend the range of the fit to |t|>10⁻². The correction terms are asymmetric giving −1·15±0·25 as the ratio of the amplitudes of the lowest order correction terms,D andD′ above and belowT _c. This value is in agreement with the recent predictions of the renormalisation group theory.     

<Emphasis Type="Italic">T</Emphasis>-odd angular correlations in the emission of prompt gamma rays and neutrons in nuclear fission induced by polarized neutrons

Study of the T-odd three-vector correlation in the emission of prompt neutrons from ²³⁵U fission by polarized cold neutrons has been continued at the facility MEPHISTO of the FRM II reactor (Technical University of Munich). The sought correlation was not found within experimental error of 2.3 × 10⁻⁵. The upper limit for the asymmetry coefficient has been set to |D _n | < 6 × 10⁻⁵ at 99% confidence level, whereas for ternary fission correlation coefficient D _α = (170±20) × 10⁻⁵. This limit casts doubt on a model that explains the three-vector correlation in ternary fission by the Coriolis mechanism. At the same time, five-vector correlation in the emission of prompt fission neutrons has been measured, which describes the rotation of the fissioning nucleus at the moment it breaks (ROT effect). At the angle 22.5° to the fission axis, the correlation coefficient was found to be (1.57 ± 0.20) × 10⁻⁴, while at the angle of 67.5° it is zero within the experimental uncertainty. The existence of ROT effect in the emission of prompt fission neutrons can be explained by the anisotropy of neutron emission in the rest frame of the fragment (fission fragments are aligned with respect to the axis of deformation of the fissioning nucleus), similar to the mechanism of ROT effect in the emission of prompt γ-rays.