The ratio of the quadrupole moments of the isotopes95Mo and97Mo

The spin-lattice relaxation timesT ₁ of the NMR signals of⁹⁵Mo and⁹⁷Mo in aqueous K₂MoO₄ solutions were determined by the inversion recovery technique. To separate the relaxation rates due to electric quadrupole interaction and due to magnetic dipole interaction, pure H₂O and mixtures of H₂O and D₂O were used as solvent. No dependence of the ratio of the relaxation ratesT ₁(⁹⁵Mo)/T ₁(⁹⁷Mo) on the composition of the solvent was to be detected, i.e. the relaxation due to magnetic dipole interaction may be neglected. From the ratio of the relaxation rates the absolute value of the ratio of the quadrupole moments of the molybdenum isotopes was evaluated: ¦Q(⁹⁷Mo)/Q(⁹⁵Mo)¦ = 11.4 ±0.3.     

Thermoelectric power of the vitreous electrolyte (AgI)0.79(Ag2O.B2O3)0.21

We have determined the thermoelectric power ? of the high ionic conductivity glass (AgI)_0.79(Ag₂O.B₂O₃)_0.21; ? is negative throughout the investigated T range, 320–500 K. The heat of transport of the mobile Ag⁺, Q_Ag, taken as the slope of the straight line fitting ? versus 1/T, is quite lower than the activation energy obtained from conductivity data, viz. Q_Ag = 2.81 kcal/mole^-1 < E_act = 4.34 kcalmole^-1. To circumvent this discrepancy, the analysis of the experimental data is carried out as follows: (i) it is supposed that Q_Ag = E_act in agreement with the free ion theory for solid electrolytes; (ii) the vibrational part of the silver ion entropy, S(Ag⁺, vib), is assumed to be equal to the entropy of silver, S(Ag); (iii) on the ground of a structural model for this kind of glasses, the ideal configurational entropy of the mobile Ag⁺, S(Ag⁺, conf)_id, is evaluated through a statistical approach. The ideal ionic entropy is defined as S(Ag⁺)_id = {S(Ag⁺, vib) + S(Ag⁺, conf)_id}; (iv) the difference {S(Ag⁺)_exp - S(Ag⁺)_id} is viewed as an excess entropy and is described according to the classical model of the regular solutions.     

VOxH2O (x= 1——-5)团簇的结构及稳定性研究

用密度泛函理论(DFT),在B3LYP/DZP水平上对H₂O分子与VO_x形成的团簇VO_xH₂O (x= 1---5)进行结构优化、能量和频率的计算,研究了团簇的稳定结构、稳定性和频率特性.结果表明VO_xH₂O (x= 1---5) 团簇的基态构型的电子态均为²A, 对称性均属C₁对称点群,其中x= 1, 4, 5时基态构型中水分子已被解离.水分子倾向于吸附在团簇VO_x上, 形成VO_xH₂O (x= 1---5)团簇. VO_xH₂O (x= 1---5)团簇中, VO_xH₂O (x= 1,4,5) 的化学活性小于VO_xH₂O (x= 2, 3)的化学活性.此外, H₂O体系与VO_x之间的结合强弱顺序为 VO₄H₂O > VO₅H₂O > VOH₂O > VO₃H₂O > VO₂H₂O. VOH₂O中离解出H原子的能量为2.88 eV和从VO₅H₂O中离解出OH基团的能量为2.38 eV, 均在可见光能量范围内,这两个化学过程有可能在可见光催化条件下进行.可以通过团簇的红外和拉曼谱特征, 初步判断水分子在VO_xH₂O团簇中是否离解.     

Heat capacity and thermodynamic properties of α-Fe2O3 in the region 300–1050 K. antiferromagnetic transition

The heat capacity of synthetic α-Fe₂O₃ has been measured in the range 300–1050K by adiabatic shield calorimetry with intermittent energy inputs and temperature equilibration in between. A λ-type transition, related to the change from antiferro- to paramagnetism in the compound, is delineated and a maximum heat capacity of about 195 JK^?1 mole^?1 is observed over a 3 K interval around 955 K. Values of thermodynamic functions have been derived and C_P (1000K), [H⁰(1000K)-H⁰(0)], and [S⁰(1000K)-S⁰(0)] are 149.0JK^?1 mole^?1, 115.72 kJ mole^?1, and 252.27 JK^?1 mole^?1, respectively, after inclusion of earlier low-temperature results [X⁰ (298.15K)-X⁰(0)]. The non-magnetic heat capacity is estimated and the thermodynamic properties of the magnetic transition evaluated. The results are compared with spin-wave calculations in the random phase approximation below the Néel temperature and the Oguchi pair model above. An upper estimate of the total magnetic entropy gives 32.4JK^?1 mole^?1, which compares favorably with that calculated for randomization of five unpaired electron spins on each iron, ΔS = 2R ln 6 = 29.79 JK^?1 mole^?1 for α-Fe₂O₃. The critical exponent α in the equation $\text{C}{}_{\mathrm{m}}\text{= (}\text{A}\text{α}\text{) [(|T}{}_{\mathrm{<mtext>n</mtext>}}\text{?T|/T}{}_{\mathrm{<mtext>n</mtext>}}\text{)?1]}{}^{\mathrm{?\alpha }}\text{+ B}$ is ?(0.50±0.10) below the maximum and 0.15±0.10 above, for T_n = 955.0K. The high temperature tail is discussed in terms of short range order.     

Nd1.85Ce0.15CuO4－δ单晶c-轴方向电阻的低场行为

采用自助熔剂缓冷法成功地生长出了Nd_1.85Ce_{0. 15}CuO_4-δ单晶，其零场下零电阻温度约为21K. 在0—0.5T范围内分别测量了磁场平行和垂直样品表面的电阻转变曲线以及0.5T不同角度下的电阻转变曲线. 结果显示磁场平行和垂直样品表面时的转变温度T_p随磁场的变化均服从H=H₀(1-T_p(h)/T_p(0))²关系. 0.5T 关键词： 1.85Ce_0.15CuO_4-δ单晶')" href="#">Nd_1.85Ce_0.15CuO_4-δ单晶 输运性质     

The twistM λ,T=0 giant modes in spherical nuclei

The theory of twisting nuclear vibrations developed by Holzwarth and Eckart to elucidate the nature of the 2^? giant mode is extended to high-multipole, spin-independentM λ,T=0 resonances. Within the framework of the distorted Fermi-surface model the parameters of inertia and stiffness against multipolarity for the nuclear incompressible Fermi-drop are derived. The energies and probabilities of the twistingM λ,T=0 modes calculated in fact without adjustable constants readE(M λ)=?ω _F \(\left[ {\frac{{(2\lambda + 3)(\lambda - 1)}}{5}} \right]^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-0em} 2}} \) andB(M λ) = γ_λ Z² A ^(2λ-4)/3 μ² fm^(2λ-2)respectively. The comparison with data for the 2^? resonance and predictions for higher multipoles are presented.     

Structural characterisation of [Cu2(bptd) (H2O) Cl4] and [Ni2(bptd)2(H2O)4] Cl4·3H2O; evidence of null intramolecular exchanges by EPR and magnetic measurements

Using the 2,5-bis(2-pyridyl)-1,3,4-thiadiazole (bptd), we recently prepared [Cu₂(bptd) (H₂O) Cl₄] and [Ni₂(bptd)₂ (H₂O)₄] Cl₄, 3H₂O in which the magnetic centres are connected through one diazine+one chloro and two diazine ligand bridges, respectively. These two compounds are the first examples that show null intramolecular magnetic interactions despite M-M distances close to 3.7 Å within perfectly planar edifices:Down to , [Cu₂(bptd)Cl₄(H₂O)] is paramagnetic while, below T_t, half of the Cu²⁺ions interact, leading to residual paramagnetism of one Cu²⁺/f.u. Magnetic susceptibility measurements, EPR and pulsed EPR study indicate the original intermolecular nature of AF exchanges.[Ni₂(bptd)₂(H₂O)₄]Cl₄·3H₂O susceptibility obeys a Curie-law involving pure paramagnetism. Moreover, its EPR spectrum can be interpreted on the basis of virtual S=1 monomers. Below 70 K, Zero Field Splitting (D∼275 G) due to dipolar interactions without magnetic exchanges could be responsible for the LT spectra splitting. For both compounds, the thia role is suggested as partially responsible for the null-in-plane magnetic exchanges.     

Study of ion–solvent interactions and activation energy of LiBr in DMSO,H<Subscript>2</Subscript>O and DMSO–H<Subscript>2</Subscript>O mixtures at various temperatures

The Jones–Dole B coefficients of the electrolyte Lithium bromide (LiBr), reference salts tetra butyl ammonium tetra phenyl borate (BU₄NBPh₄), tetra butyl ammonium bromide (BU₄NBr), and potassium chloride (KCl) in dimethylsulfoxide (DMSO), water, and DMSO–water mixtures were obtained at different temperatures range from 25 to 45 °C For this, the relative viscosities were measured for Lithium bromide (LiBr) and reference salts in DMSO, water, and DMSO–water mixtures at above-mentioned temperatures. The B coefficients of these electrolytes were behaved as structure makers in DMSO, while in H₂O and DMSO–H₂O mixtures, the B-coefficient values were less positive showing the weak structure-making effect. Ionic viscosity B coefficients allow us to assess the behavior of ions in the solvent mixtures. In this study it was observed that all the values of ionic B coefficient of (Li⁺) were positive and small showing the weak structure-making effects. It was also observed that Br⁻ ions maintain negative B coefficient values in all DMSO–H₂O mixtures, except in 60% DMSO mole fraction. From this it can be concluded that Br⁻ ion behaved as a structure breaker in water and in all DMSO–H₂O mixtures except in 60% DMSO mole fraction mixtures. The low B _± values of alkali metal ions and Br⁻ ions in water are due to the breakdown of the tetrahedral structural of water and the formation of strongly structured solvated ion. It is also observed that the values of the energy of activation of the flow for LiBr are greater in DMSO–water mixtures and in pure water than in DMSO. This may be due the presence of a network of hydrogen bonds which cause the hindrance in the flow of the solution of LiBr in DMSO–water mixtures and in pure water than in DMSO.     

Crystal-field analysis for d ions at D4h symmetry sites: Electronic states in trans-NiCl2(H2O)4 complex

The polarized absorption spectra of trans-NiCl₂(H₂O)₄ complex were measured by Bussière et al. [Coord. Chem. Rev. 219-221 (2001) 509-543] at low-temperature. Using the experimental spectroscopic data, semiempirical calculations of the crystal-field levels of trans-NiCl₂(H₂O)₄ chromophore are carried out, based on the Racah theory. We used idealized D_4h point group symmetry to analyse the observed crystalline-field splitting of this chromophore. As a result, Racah and crystal-field parameters have been reliably obtained. A good agreement between the theoretical and experimental energy levels of trans-NiCl₂(H₂O)₄ complex has been obtained. The region of ³T_1g/¹E_g(O_h) bands is of great interest and it is useful to use the tetragonal symmetry to understand the features of this spectral region.     

Experimental determination of the electron screening potential energy for the d(d, n)3He Reaction in ZrD2 and D2O in the ultralow energy region

This work is devoted to measuring of the values of the astrophysical S-factors and electron screening potential energy for a d(d,n)³He reaction occurring at ultralow energies in zirconium deuteride ZrD₂ (3.5–7.0 keV) and heavy water D₂O (2.2–6.0 keV). The experiment was performed on the Hall pulsed plasma accelerator at the TPU Nuclear Physics Institute (Tomsk) with ZrD₂ and D₂O targets produced by the magnetron sputtering of zirconium in a deuterium environment and heavy water freezing-out on a copper support, respectively. A χ ² analysis of the dependence of the neutron yields and astrophysical S-factors for the dd reaction on the deuteron collision energy E revealed that the upper bounds of the electron screening potential energy for interacting deuterons in ZrD₂ and D₂O and of the astrophysical S-factors at the deuteron collision energy E = 0 were U _e (ZrD₂) < 30 eV, U _e (D₂O) < 25 eV, S(0) = (57.2 ± 3.9) keV · b (ZrD₂), S(0) = (58.6 ± 3.6) keV · b (D₂O) at the 90% confidence level.     

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.     

A型超导体的近似临界温度公式(Ⅰ)——μ*=0情形

本文用数值解方法从Eliashberg方程计算出超导临界温度T_c,并考察T_c对有效声子谱的依赖关系。在这个研究中,a²F(ω)被取为双δ函数谱,并允许其中的谱参数可以在很宽范围内改变。作者发现在λ<∧区域(即在T_c级数解的收敛圆外),T_c除了依赖λ和矩比外,还依赖T_c级数解的收敛半径倒数Λ;它们之间的关系是有规律的。在这些结果的启示下,本文在μ^*=0情形,用弥合数值解的方法得到一个适用于λ<Λ区域的T_c近似公式。接着,本文作者对吉光达和吴杭生的一篇文章进行了研究,指出:该文提出的超导体分类建议及其工作的主要结论是对的。但其中对决定A型超导体临界温度主要参量问题进行的分析,只适用于这样一些A型超导体,它们的收敛半径倒数Λ或者比λ₀小,或者虽比λ₀大、但λ又小于λ₀,其中λ₀是个依赖谱形状的参量,它的定义在正文中给出。对另一些A型超导体(λ₀<λ<Λ),决定T_c的主要参量不再是λ,而是δ=1/∧^0.5(ω_1/2/ω_log)^5.5λ^1.55。 关键词：     

Flicker noise of hot electrons in silicon at T = 78 K

From flicker-noise and current-voltage measurements performed on an n⁺nn⁺ silicon planar device at T = 78 K we calculated Hooge's parameter α as a function of the electric field strength, E₀. We found that α(E₀) = α(0)/[1 + (E₀/E_c)²]. E_c is a critical field where the drift velocity equals the sound velocity, indicating the connection of the observed effect with acoustical phonon scattering.     

Investigation of the mass dependence of self-diffusion coefficients by molecular dynamics calculations: comparison with the Enskog theory

The dependence of the Enskog self-diffusion coefficients D_i,E on mass ratios m_i* = m_i/m₁ in hard sphere mixtures is described by exponential expressions of the form D_i,E = D⁰ _i,E(m*₂)eX_i,E in the case of binary mixtures and D_i,E = D⁰ _iE (m*₂)eX_i,E(m*₃)eXt_i,E in the case of ternary mixtures. D⁰ _i,E are the self-diffusion coefficients in reference mixtures with m*₂ = m*₃ = 1. ex_i,E (i = 1,2) and ext_i,E (i = 1,2,3) are the so called Enskog exponents of binary and ternary mixtures, respectively. Their dependence on particle mass and diameter, mole fraction, density and temperature is discussed and compared with corresponding results of molecular dynamics calculations.     

A calorimetric study of the dimerized phase of C60 fullerene

The temperature dependence of the heat capacity at a constant pressure C _p ⁰ = f(T) for the dimerized phase of the C₆₀ fullerene in the temperature range 300–575 K and the thermodynamic characteristics for depolymerization of this phase under normal pressure are investigated using precision differential scanning calorimetry. It is established that thermal depolymerization is a kinetically hindered process. The final products of thermal depolymerization are identified as a partially crystalline monomer face-centered cubic phase of C₆₀ with a degree of crystallinity α = 67 mol %. The results obtained in this study and our previous experimental data on the low-temperature heat capacity are used in the calculations of standard thermodynamic functions for the (C₆₀)₂ crystalline dimer, namely, the heat capacity C _p ⁰ (T), the enthalpy H ⁰(T) ? H ⁰(0), the entropy S ⁰(T), and the Gibbs function G ⁰(T) ? H ⁰(0) in the temperature range from T → 0 to 394 K.     

Thermodynamic study of compounds of the Nd-Ba-Cu-O system

Standard enthalpies of formation for solid solutions of composition Nd_{1 + x} Ba_{2 ? x} Cu₃O _y (x = 0–0.8, y = 6.65–7.24) from oxides were determined by solution calorimetry. The heat capacity of NdBa₂Cu₃O_6.87 phase was measured in the range 5–320 K by low-temperature adiabatic calorimetry. The absolute entropy S ^o(T), the difference of enthalpies H ^o(T)-H ^o(0 K), and the reduced Gibbs energy Φ^o(T) = S ^o(T)–[H ^o(T)–H ^o(0)]/T were calculated on the basis of smoothed dependence C _p (T) in the 0–320 K range. An assessment was made for the heat capacities and the absolute entropies of solid solutions Nd_1+x Ba_2?x Cu₃O _y . The obtained set of thermodynamic parameters can be used for the calculation of phase equilibria in the Nd-Ba-Cu-O system.     

Inhomogeneous state of the electron system in the Sr14 ? x Ca x Cu24O41 superconducting cuprate: 63Cu-17O NMR study

Charge fluctuations in quasi-one-dimensional hole-doped Sr₁₄Cu₂₄O₄₁ (Ca-0) and Sr₂Ca₁₂Cu₂₄O₄₁ (Ca-12) spin-ladder cuprates have been studied with the use of ⁶³Cu-¹⁷O NMR. Spin-echo decay rates ¹⁷(1/T ₂) and ⁶³(1/T ₂) have been measured in the temperature range of T = 10–300 K. The variation of ¹⁷(1/T ₂) and ⁶³(1/T ₂) in the Ca-0 compound is monotonic in the entire temperature range of the NMR study. In the Ca-rich compound, pronounced peaks have been observed in the decay rates ¹⁷(1/T ₂) and ⁶³(1/T ₂) at temperatures of 25 and 50 K, respectively. This result indicates the presence of collective low-frequency (τ_c ∼ T ₂) charge density fluctuations in superconducting Ca-12 with an activation energy of E _A = 100(10) K. The fluctuations gradually slow down as the temperature decreases. The amplitude of the charge density fluctuations is only 0.01–0.02 hole per site. ¹⁷O-⁶³Cu spin-echo double-resonance (SEDOR) experiments in Sr_{14 − x} Ca _x Cu₂₄O₄₁ oxides with x = 0 and 12 have been performed depending on the temperature and orientation of single crystals in a magnetic field. The constants of an indirect heteronuclear ¹⁷O-⁶³Cu interaction of nuclear spins mediated by conduction electrons have been measured. The estimates of the indirect interaction constants for nearest neighbors O1-Cu and O2-Cu, as well as SEDOR experiments with selective excitation of separate sections of ¹⁷O and ⁶³Cu NMR spectra, provide convincing evidence of the microscopically inhomogeneous spatial distribution of spin density developing in a crystal. Original Russian Text ? Yu.V. Piskunov, V.V. Ogloblichev, S.V. Verkhovsky, 2007, published in Pis’ma v Zhurnal éksperimental’noĭ i Teoreticheskoĭ Fiziki, 2007, Vol. 86, No. 11, pp. 850–855.     

Features of Propene Oxidation in Argon,Carbon Dioxide and Water Vapor Media at a High Density of Reagents

The features of propene oxidation in high-density mixtures of C₃H₆/O₂ ([C₃H₆]₀ = 0.23–0.25 mol/dm³, [O₂]₀ = 0.76–0.82 mol/dm³), diluted with argon, carbon dioxide and water vapor at uniform heating (1 K/min) to T ≤ 620 K are investigated for the first time. From the time dependences of reaction mixtures temperature it is found that propene self-ignition occurs at 465 K and does not depend on the nature of the diluent. Using mass spectrometry analysis it is demonstrated that in the composition of the products of propene oxidation in the Ar and CO₂ medium predominate methanol, acetaldehyde, acetone, acetic acid and formaldehyde; in the oxidation in the H₂O medium, only small amof O₂ in the oxidation of propene increases in ounts of these substances were registered. Degree of consumption the following order: CO₂ ? Ar < H₂O, which is a consequence of the involvement of CO₂ and H₂O molecules in chemical transformations. Mechanisms of the observed processes are discussed.     

Superconducting and magnetic properties of La3−x In Cex

Measurements of the critical temperature, T_c(x), the critical field, H_c2(x,T) and the susceptibility, χ (T), as a function de la concentration, x, in the system La₃₋x Ce_xIn, are compared with the theories of Muller-Hartmann and Zittsrtz, and Abrikosov and Gor'kov. The H_c2(x, T = 0) and χ(T) measurements indicate the appearance of short range antiferromagnetic order around x = 0.04 which is probably responsible for the anomalous behavior of T_c(x).     

Effect of chirality on the dynamics of domain walls in the molecular ferrimagnet [MnII(HL-pn)(H2O)][MnIII(CN)6] · 2H2O

The contributions from modes of switching, sliding, creep, and Debye relaxation of pinned domain walls to the low-frequency magnetic properties of the chiral and racemic molecular ferrimagnets [Mn^II(HL-pn)(H₂O)][Mn^III(CN)₆] · 2H₂O have been separated. It has been found that the chirality of the atomic and spin structures affects the temperatures of the transitions from the sliding mode to the creep mode and from the creep mode to the mode of Debye relaxation. In the chiral crystals, transitions to the creep and Debye relaxation modes have been observed at temperatures T = 7 and 5 K, respectively. In the racemic crystals, these transitions have been observed at temperatures T = 13 and 9 K, respectively, all other factors being equal.