Reactions of initiation of the autoignition of H<Subscript>2</Subscript>–O<Subscript>2</Subscript> mixtures in shock waves

The initiation of the autoignition of hydrogen–oxygen–argon mixtures behind reflected shock waves is studied by absorption and emission spectrophotometry in the temperature range of 960 < T < 1670 K at pressures of ~0.1 MPa. Introduction of Mo(CO)₆ additive in an amount of ~80 ppm made it possible to study the effect of O atoms on the shortening of the ignition delay time of H₂–O₂–Ar mixtures. A kinetic modeling of our own and published experimental data at temperatures of 930 < T < 2500 K and pressures of 0.05 < P < 8.7 MPa enabled to establish how the initiation reactions influence the process of self-ignition and to evaluate the rate constant for one of the initiation reactions: k(H₂ + O₂ → 2OH) = (3 ± 1) × 10¹¹exp(–E _a/RT), cm³ mol^–1 s^–1, where E _a = (40 ± 2) kcal/mol.     

Scheme of the β-decay of <Superscript>234</Superscript>Th

The scheme of the β-decay of ²³⁴Th is still not completely clear. Only the upper bound (10 keV) of the energy of the isomeric transition from level T_1/2 = 1.17 min of the ²³⁴Pa nucleus is known, and the correspondence between gamma quanta of several energies emitted in the β-decay of ²³⁴Th and specific nuclear levels of ²³⁴Pa has not been established. In this work, the isomeric transition energy of 2.6 ± 0.5 keV is determined via the γ-spectrometry of a ²³⁴Th source in γγ-coincidences, and a new ²³⁴Pa level populated in the β-decay of ²³⁴Th is introduced.     

Coercivity of homogenized ensembles of anisotropic γ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles

The influence of interaction between anisotropic γ-Fe₂O₃ nanoparticles on their coercive force H _c is studied. In samples where the degree of homogenization of anisotropic γ-Fe₂O₃ nanoparticles is high owing to mechanical, ultrasonic, and magnetic dispersion with subsequent filtering of resulting suspensions, H _c is almost independent of volume concentration η of the particles when η varies between 4 × 10⁻⁴ and 10⁻¹. In samples homogenized only mechanically, the H _c versus logη dependence is linear.     

Mössbauer studies of stoichiometry of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>: characterization of nanoparticles for biomedical applications

The iron oxide Fe₃O₄, the mineral magnetite sometimes called ferrosoferric oxide, is notoriousy non-stoichiometric even in bulk form so its formula may be written Fe_3?δO₄. In nanoparticle form, where it has applications in medicine and information technology, it is even more susceptible to oxidation. In this paper we report synthesis and studies of superparamagnetic Fe₃O₄ nanoparticles with controlled diameters of 5.3, 10.6 and 11.9 nm. In room temperature spectra, departures from stoichiometry δ of up to 0.02 were estimated from the relative amounts of Fe ³⁺/ Fe ²⁺ and from their isomer shifts. This cannot be used for very small particles of diameter 10.6 nm and less as they are superparamagnetic at room temperature and do not show hyperfine splitting owing to fast relaxation. Such particles have promise for use in enhancing MRI signals. The magnetic spectrum is restored by the application of a relatively small magnetic field (10 kG). As the temperature is lowered the relaxation slows down and 6-line magnetic hyperfine patterns appear below a blocking temperature T_B. The values of T_B obtained are lower than those of many other researchers reported in the literature, suggesting that our particles are less affected by magnetic interactions between them. At low temperatures all the spectra are similar and closely resemble that of bulk Fe₃O₄ confirming that departures from stoichiometry are small.     

Study of phase transition of TiO<Subscript>2</Subscript>–CaO system

Electrical conductivity of TiO₂ doped with CaO has been measured at different temperatures for various molar ratios. The conductivity after initially remaining constant till about 140 °C increases with temperature due to the migration of vacancies created by doping. After attaining a maximum value at 240 °C, conductivity decreases due to the collapse of fluorite framework. A second rise in conductivity at high temperature beyond 400 °C indicates the phase transition of TiO₂, from anatase to rutile, which is confirmed by the differential scanning calorimetry results. X-ray powder diffraction, impedance measurements, and Fourier transform infrared spectral studies were also carried out for confirming the doping effect and phase transitions in TiO₂. Doping of TiO₂ with CaO shifts the transition to lower temperatures.     

Determination of the region of existence of ferromagnetic nanostructures in the paraphase of La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ba<Subscript>x</Subscript>MnO<Subscript>3</Subscript> by the EPR method

In the paraphase of a number of La_1?x Ba_xMnO₃ single crystals with 0.1 ≤ x ≤ 0.2 below 340 K, signals of the ferromagnetic resonance are observed, which indicates the presence of magnetically ordered nanoscopic objects (ferrons). The region of the existence of ferrons on the Ba density-temperature phase diagram has an approximate triangular shape, which is characteristic of the Griffiths phase. Investigations of the angular and frequency dependences of the position of the ferromagnetic resonance line indicate that the nanostructures have a spherical shape. The parameters of their magnetic anisotropy are found to be H _a1 = 2500 Oe and H _a2 = ?700 Oe.     

Influence of Morphological Defects on Thermophysical Properties of γ-Gd<Subscript>2</Subscript>S<Subscript>3</Subscript>

The temperature dependences of the heat capacity (C _p ) and the thermal conductivity (κ) in the temperature range from 300 to 773 K of polycrystalline gadolinium sulfide samples (γ-GdS _y ) with the deviation of the composition from the integer stoichiometric were studied. It was found that the thermal conductivity of gadolinium sulfides decreases monotonically and reaches 0.74 W/(m K) at T = 773 K for the composition y = 1.479, which is much lower than for the known single-crystal samples. The influence of morphological defects (boundaries of crystallites and dislocations) on the intensity of scattering of phonons is studied. It has been established that ceramic samples of gadolinium sulphides have a large heat capacity and a lower thermal conductivity, in comparison with monocrystalline samples of the same composition.     

Measurement of the Dalitz-decay branching ratio of the π<Superscript>0</Superscript>

The ratio is measured by comparing the production rates of the π⁰ in the two decay channels. The analysis is based on approximately four million hadronic decays of the Z boson recorded by the ALEPH detector in the years 1991 to 1995. The value of is determined to be . A recalculation of the Particle Data Group world average gives rise to a slightly improved error, and moves the world average closer to the theoretical value.     

Photoacoustic method of determination of quantum efficiency of luminescence in Mn<Superscript>2+</Superscript> ions in Zn<Subscript>1−x−y</Subscript>Be<Subscript>x</Subscript>Mn<Subscript>y</Subscript>Se crystals

This paper presents step by step the procedure of determination of the quantum efficiency of luminescence of Mn²⁺ ions in the Zn_1−x−yBe_xMn_ySe crystals. The method is based on the photoacoustic spectroscopy approach. In the paper, the experimental spectra of absorbance, transmission, absorption and photoacoustic spectra of the samples are presented and analyzed from the point of view of the possibility of determination of the quantum efficiency of Mn²⁺ ion luminescence at room temperature. It was determined experimentally that in the investigated crystals the quantum efficiency of luminescence in the Mn²⁺ ions is about 35%, 40%, 32% for the absorption peaks at 430 nm, 470 nm, and 510 nm, respectively, for Zn_0.75Be_0.2Mn_0.05Se crystal.     

Perturbative analysis of the 2νββ decays of <Superscript>100</Superscript>Mo and <Superscript>116</Superscript>Cd

We have performed a theoretical analysis of the ground-state-to-ground-state transitions in ¹⁰⁰Mo and ¹¹⁶Cd, based on the quasiparticle random-phase approximation and on a straightforward perturbative scheme. The results show that the single-state dominance found in the realistic calculations of the nuclear matrix elements, which is consistent with data, can be viewed as a result of the interference between few two-quasiparticle configurations. Received: 12 August 2002 / Accepted: 23 October 2002 / Published online: 18 February 2003 RID="a" ID="a"e-mail: civitarese@fisica.unlp.edu.ar Communicated by V.V. Anisovich     

AC conductivity and dielectric behavior of low-temperature phase of α-AgCuPO<Subscript>4</Subscript>

The copper monophosphate compound, α-AgCuPO₄, was prepared by the conventional solid-state reaction. The purity of the compound was checked by X-ray diffraction technique (XRD). Detailed dielectric and electrical properties of the compound were analyzed as a function of frequency (209 Hz–1 MHz) and temperature (343–514 K). The AC conductivity has been fitted and studied using Jonscher’s equation, whose exponent n varied with the temperature, showing that the overlapping large polaron tunneling model (OLPT) is the appropriate model to describe the electrical conduction mechanism.     

Formulation of the Hellmann–Feynman theorem for the “second choice” version of Tsallis’ thermostatistics

An approach to formulating the Hellmann–Feynman theorem within the “second choice” formalism of non-extensive statistical mechanics is considered. For the state of thermal equilibrium, we derive a relation of Hellmann–Feynman type between the derivative of the non-extensive free energy with respect to the external parameter and the quantum statistical q$q$-average of the derivative of the Hamilton operator. We also give a proper extension for an arbitrary observable commuting with the Hamiltonian. Some reasons for the usefulness of new formulas are discussed.     

Mössbauer study of the modulated magnetic structure of FeVO<Subscript>4</Subscript>

Mössbauer spectroscopy is used to study the FeVO₄ multiferroic, which undergoes two magnetic phase transitions at T _N1 ≈ 22 K and T _N2 ≈ 15 K. The first transition (T _N1) is related to transformation from a paramagnetic state into a magnetically ordered state of a spin density wave, and the second transition (T _N2) is associated with a change in the type of the spatial magnetic structure of the vanadate. The electric field gradient tensor at ⁵⁷Fe nuclei is calculated to perform a crystal-chemical identification of the partial Mössbauer spectra corresponding to various crystallographic positions of Fe³⁺ cations. The spectra measured in the range T _N2 < T < T _N1 are analyzed on the assumption about amplitude modulation of the magnetic moments of iron atoms μ_Fe. The results of model intersection of the spectra recorded at T < T _N2 point to a high degree of anharmonicity of the helicoidal magnetic structure of the vanadate and to elliptic polarization of μ_Fe. These features are characteristic of type-II multiferroics. The temperature dependences of the hyperfine interaction parameters of ⁵⁷Fe nuclei that were obtained in this work are analyzed in terms of the Weiss molecular field model on the assumption of orbital contribution to the magnetic moments of iron cations.     

Study of complex impedance spectroscopic properties of the α-NaCuPO<Subscript>4</Subscript> compound

In the present study, α-NaCuPO₄ compound was prepared by solid-state reaction method and characterized by X-ray powder diffraction and infrared spectroscopy. The AC electrical conductivity and dielectric relaxation properties of this compound have been investigated by means of impedance spectroscopy measurements over a wide range of frequencies and temperatures 209 Hz–1 MHz and 598–708 K, respectively. Both impedance and modulus analysis exhibit the grain and grain boundary contribution in the electrical response of the sample. It was found that the data of the AC measurements follow the overlapping large polaron tunneling model and the model’s parameters were determined.     

Calculation of line parameters of the ν<Subscript>3</Subscript> band of monodeuterated methane: Nitrogen broadening

Halfwidths and shifts of CH₃D lines are calculated for the case of nitrogen broadening. The calculations are performed for room temperature (296 K) for vibrational–rotational lines in the ν₃ parallel band, with the rotational quantum numbers varying in the ranges of 0 ≤ J ≤ 70 and 0 ≤ K ≤ 20. For each line, the temperature-dependence characteristics are calculated in the range of 200–400 K recommended for the HITRAN database. The calculations are carried out using a semiempirical method with a correction factor the parameters of which are adjusted on a number of experimental values.     

Emission spectroscopy of the A<Superscript>1</Superscript>Π–X<Superscript>1</Superscript>Σ<Superscript>+</Superscript> system of AlH

The high-resolution emission spectrum of the A¹ Π–X¹Σ⁺ transition of AlH was observed in the 18 000–25 000 cm^-1 spectral region using a conventional spectroscopic technique. The AlH molecules were excited in an Al hollow-cathode lamp filled with a mixture of Ne carried gas and a trace amount of NH₃. The emission from the discharge was observed with a plane grating spectrograph and recorded by a photomultiplier tube. In total 163 transition wave numbers belonging to six bands (0-0,1 and 1-0,1,2,3) were precisely measured and rotationally analysed. In the final fit the present data have been combined with available high-resolution measurements of the vibration-rotation bands by White et al. [J. Chem. Phys. 99, 8371 (1993)]. This procedure enabled extracting molecular constants for the A¹ Π and X¹ Σ⁺ states of AlH. A very slight local perturbation has been discovered in the v=1 vibration level of the A¹ Π state at J=5. This was probably caused by the interaction with the a³Π state.     

Broadening and shift of lines of the ν<Subscript>2</Subscript> + ν<Subscript>3</Subscript> band of water vapor induced by helium pressure

The broadening and shift coefficients of more than 100 absorption lines of the ν₂ + ν₃ band of water vapor that are induced by the pressure of helium are measured and calculated. The broadening and shift coefficients are obtained from analysis of the room-temperature absorption spectra of an H₂O-He mixture measured with a resolution of 0.007 cm^?1 on a Fourier spectrometer in a large range of helium pressures. The specific features in the rotational dependence of the line center shifts are determined, which, in contrast to the broadening induced by other gases, are mainly positive. The calculated coefficients of the line broadening and shift of line centers are determined by a semiclassical method. An unusual dependence of the shift coefficients is explained by the rotational dependence of the intermolecular isotropic interaction potential.     

Theoretical study of the structure of lead zirconate–titanate PbZr<Subscript>0.6</Subscript>Ti<Subscript>0.4</Subscript>O<Subscript>3</Subscript>

A model of the structure of the piezoelectric ceramic lead zirconate–titanate PbZr_1–x Ti _x O₃ (PZT) is proposed. The model is based on ab initio calculations for possible local structures using the density functional theory (DFT) approach. A comparison of the calculated neutron diffraction data for local structures and the measured diffraction data obtained for actual powder samples shows there is a partially established long-range crystalline order in the material, in the sublattice of Zr and Ti cations.