New High-Resolution Analysis of the nu(3) Band of the (15)N(16)O(2) Isotopomer of Nitrogen Dioxide by Fourier Transform Spectroscopy

New high-resolution Fourier transform absorption spectra of an (15)N(16)O(2) isotopic sample of nitrogen dioxide were recorded at the University of Bremen in the 6.3-μm region. Starting from the results of a previous study [Y. Hamada, J. Mol. Struct. 242, 367-377 (1991)], a new and more extended analysis of the nu(3) band located at 1582.1039 cm(-1) has been performed. The spin-rotation energy levels were satisfactorily reproduced using a theoretical model which takes into account both the Coriolis interactions between the spin-rotation energy levels of the (001) vibrational state with those of the (020) and (100) states and the spin-rotation resonances within each of the NO(2) vibrational states. Precise vibrational energies and rotational, spin-rotation, and coupling constants were obtained in this way for the first triad of (15)N(16)O(2) interacting states {(020), (100), (001)}. Finally, a comprehensive list of line positions and line intensities of the {nu(1), 2nu(2), nu(3)} interacting bands of (15)N(16)O(2) was generated, using for the line intensities the transition moment operators which were obtained previously for the main isotopic species. Copyright 2000 Academic Press.     

GaNxAs1-x(x＜0.01)中合金态的光学特性

应用多种光谱手段研究了分子束外延生长在半绝缘的(001)GaAs衬底上的低氮含量的GaNAs中三元合金态的光学特性．变温PL谱揭示了合金态的本征特性以及其与氮的杂质态的根本区别，而脉冲激发的光荧光谱则进一步显示了合金态的本征光学特性．最后还研究了GaNAs的吸收光谱特征．     

Nitrogen-15 fractionation in the thermal decomposition of nitrous oxide of natural isotopic composition

The 15N fractionation in the thermal decomposition of nitrous oxide (N2O) of natural isotopic composition has been investigated in quartz reaction vessel in the temperature interval 888-1073 K. The formulas relating the observed experimentally 15N fractionations with the primary 15N kinetic isotope effect, (k14/k15)p for 14N15N16O, and secondary 15N kinetic isotope effect, (k14/k15)s for 15N14N16O, have been derived. The experimentally estimated 15N kinetic isotope effects have been compared with the primary and secondary 15N kinetic isotope effects calculated with the absolute rate theory formulations applied to linear three atom molecules. A good agreement was found for the primary 15N kinetic isotope effect, (k14/k15)p, in the temperature interval 888-1007 K. But at 1073 K the decompositions of N2O, accompanied by NO (nitric oxide) formation proceed with a twice times smaller primary kinetic isotope effect, (k14/k15)p of 1.0251 +/- 0.0009, only, suggesting the nonlinear transition state structures with participation of the fourth external atom at high temperature decompositions of nitrous oxide. The nitrogen isotope effects determined in this study correlate well with nitrogen isotope fractionations observed in the natural biological, earth and atmospheric processes.     

15N Analysis of nitric oxide and nitrous oxide by cryotrap enrichment using a gas chromatograph quadrupole mass spectrometer and its application to (15)N-tracer investigations of NO/N(2)O formation in soil

Nitric oxide (NO) and nitrous oxide (N(2)O) are two important trace gases in the atmosphere. Determining the concentration and (15)N abundance of NO and N(2)O in air is difficult owing to their very low concentration in the atmosphere (NO < 1 ppb(v); N(2)O approximately 0.32 ppm(v)). Although (15)N analysis of N(2)O in ambient concentrations can be carried out using a gas chromatograph quadrupole mass spectrometer system (GC-QMS) and a dosage of 2 mL of air by means of a sample loop, this system is not sensitive enough to measure the ambient concentration of NO and its (15)N abundance. Therefore the concentration of NO must be enriched by cryotrapping (cooling with liquid nitrogen). The (15)N analytical method developed enables the sensitive and sufficiently precise measurement of (15)N-enriched NO in air. Furthermore, the analytical equipment developed greatly improves existing (15)N(2)O analysis using the GC-QMS technique. An application of the (15)N analysis method will be shown for an investigation on the NO and N(2)O formation in black earth soil after (15)NH(4)(+), (15)NO(3)(-) and (15)NO(2)(-) labelling. Copyright 1999 John Wiley & Sons, Ltd.     

From stable divalent to valence-fluctuating behaviour in Eu(Rh(1-x)Ir(x))2Si2 single crystals

We have succeeded in growing high-quality single crystals of the valence-fluctuating system EuIr(2)Si(2), the divalent Eu system EuRh(2)Si(2) and the substitutional alloy Eu(Rh(1-x)Ir(x))(2)Si(2) across the range 0 < x < 1, which we characterized by means of x-ray diffraction, energy-dispersive x-ray spectroscopy, specific heat, magnetization and resistivity measurements. On increasing x, the divalent Eu ground state subsists up to x = 0.25 with a slight increase in Néel temperature, while for 0.3≤x < 0.7 a sharp hysteretic change in susceptibility and resistivity marks the first-order valence transition. For x?0.7 the broad feature observed in the physical properties is characteristic of the continuous valence evolution beyond the critical end point of the valence transition line, and the resistivity is reminiscent of Kondo-like behaviour while the Sommerfeld coefficient indicates a mass renormalization of at least a factor of 8. The resulting phase diagram is similar to those reported for polycrystalline Eu(Pd(1-x)Au(x))(2)Si(2) and EuNi(2)(Si(1-x)Ge(x))(2), confirming its generic character for Eu systems, and markedly different to those of homologue Ce and Yb systems, which present a continuous suppression of the antiferromagnetism accompanied by a very smooth evolution of the valence. We discuss these differences and suggest them to be related to the large polarization energy of the Eu half-filled 4f shell. We further argue that the changes in the rare earth valence between RRh(2)Si(2) and RIr(2)Si(2) (R = Ce, Eu, Yb) are governed by a purely electronic effect and not by a volume effect.     

Evidence for a transition in the pairing symmetry of the electron-doped cuprates La(2-x)Ce(x)CuO(4-y) and Pr(2-x)Ce(x)CuO(4-y)

We present measurements of the magnetic penetration depth, lambda(-2)(T), in Pr(2-x)Ce(x)CuO(4-y) and La(2-x)Ce(x)CuO(4-y) films at three Ce doping levels, x, near optimal. Optimal and overdoped films are qualitatively and quantitatively different from underdoped films. For example, lambda(-2)(0) decreases rapidly with underdoping but is roughly constant above optimal doping. Also, lambda(-2)(T) at low T is exponential at optimal and overdoping but is quadratic at underdoping. In light of other studies that suggest both d- and s-wave pairing symmetry in nominal optimally doped samples, our results are evidence for a transition from d- to s-wave pairing near optimal doping.     

Spin-reorientation, ferroelectricity, and magnetodielectric effect in YFe(1-x)Mn(x)O3(0.1 ≤ x ≤ 0.40)

We report the observation of magnetoelectric and magnetodielectric effects at different temperatures in Mn-substituted yttrium orthoferrite, YFe(1-x)Mn(x)O(3)(0.1 ≤ x ≤ 0.40). Substitution of Mn in antiferromagnetic YFeO(3)(T(N) = 640 K) induces a first-order spin-reorientation transition at a temperature, T(SR), which increases with x whereas the Néel temperature (T(N)) decreases. While the magnetodielectric effect occurs at T(SR) and T(N), the ferroelectricity appears rather at low temperatures. The origin of magnetodielectric effect is attributed to spin-phonon coupling as evidenced from the temperature dependence of Raman phonon modes. The large magnetocapacitance (18% at 50 kOe) near T(SR) = 320 K and high ferroelectric transition temperature (～115 K) observed for x = 0.4 suggest routes to enhance magnetoelectric effect near room temperature for practical applications.     

Scaling of anomalous hall resistivity in Nd2(Mo(1-x)Nb(x))2O7 with spin chirality

We have investigated scaling of anomalous Hall resistivity with longitudinal resistivity (rho(xx)) in pyrochlore type Nd2(Mo(1-x)Nb(x))2O7 with spin chirality. Scattering rate of the conduction electron on the Mo sublattice can be varied with x from band transport to polaron hopping, while keeping the two-in-two-out structure of the Nd moments intact. The anomalous part of the Hall resistivity arising from the Mo spin chirality (rho(H)(chi)) shows a clear scaling behavior with rho(xx) (rho(H)(chi) proportional to rho(xx)0.39), in accord with a recent theoretical result based on the Berry phase mechanism in the hopping conduction regime.     

Explosive hydrogen burning of 17O in classical novae

We report on the observation of a new resonance at E(lab)(R)=190 keV in the 17O(p,gamma)18F reaction. The measured resonance strength amounts to omegagamma(pgamma)=(1.2+/-0.2)x10(-6) eV. With this new value, the uncertainties in the 17O(p,gamma)18F and 17O(p,alpha)14N thermonuclear reaction rates are reduced by orders of magnitude at nova temperatures. Our significantly improved reaction rates have major implications for the galactic synthesis of 17O, the stellar production of the radioisotope 18F, and the predicted oxygen isotopic ratios in nova ejecta.     

Air- and N(2)-Broadening Parameters of Water Vapor: 604 to 2271 cm(-1)

High-resolution measurements of air- and N(2)-broadened widths and pressure-induced frequency shifts of water vapor were obtained covering the spectral region between 604 and 2271 cm(-1). Over 1300 vibration-rotation transitions were measured including the (000)-(000), (010)-(010), (010)-(000), (020)-(010), and (100)-(010) vibrational bands of H(2)(16)O. Also included were measurements of H(2)(18)O and H(2)(17)O from normal water vapor samples and H(2)(18)O + N(2) observations with oxygen-18-enriched gas samples. Collision-narrowing effects were observed in a few lines involving high J and low K(a) transitions with the lowest measured linewidth coefficient equal to 0.0057(4) cm(-1)/atm (air-broadening) for the completely overlapping transitions, 17 0 17 <-- 18 1 18 and 17 1 17 <-- 18 0 18, at 1235.204 cm(-1). The majority of the linewidth values were derived from the measurements using a Voigt line profile. A few lines with air- or N(2)-broadened half-width values of about 0.012 cm(-1) or less were found to exhibit collision-narrowing effects and were also analyzed with a profile proposed by Galatry. The results are compared to values given in previous studies. Copyright 2000 Academic Press.     

Mg-Al-Ca合金中三元Laves相的稳定性和电子结构

采用基于密度泛函理论的第一性原理方法,应用VASP (Vienna Ab-initio Simulation Package) 计算软件,研究了Mg-Al-Ca合金中三元Laves相,即Ca(Mg1-x,Alx)2和Al2(Ca1-x,Mgx) (x=0, 0.25, 0.50, 0.75, 1)在不同形态结构(C14, C15和C36)下的相稳定性及电子结构。计算所得的晶格常数和实验值吻合很好,形成能和相关能的计算用来研究三元Laves相的合金化能力和稳定性,结果表明：C14-Ca(Mg0.25,Al0.75)2具有很好的合金化能力,而C15- CaAl2具有很好的结构稳定性。态密度和电荷密度的计算用来研究Mg-Al-Ca合金中三元Laves相稳定性的内在微观机制。     

Unusual Nernst effect suggesting time-reversal violation in the striped cuprate superconductor La(2-x)Ba(x)CuO4

The striped cuprate La(2-x)Ba(x)CuO(4) (x=1/8) undergoes several transitions below the charge-ordering temperature T(co)=54 K. From Nernst experiments, we find that, below T(co), there exists a large, anomalous Nernst signal e(N,even)(H,T) that is symmetric in field H, and remains finite as H→0. The time-reversal violating signal suggests that, below T(co), vortices of one sign are spontaneously created to relieve interlayer phase frustration.     

CexZr1-xO2固溶体储氧性能与结构的关系

采用加热回流技术制备了系列CexZr1-xO2(0.25≤x≤1)固溶体,通过N2物理吸附、XRD、Raman光谱、UV-Vis漫反射光谱表征了不同铈锆组成的铈锆复合氧化物结构对储氧性能的影响.结果表明,在铈锆组成比不同的样品之间,结构性质相差较大,随着载体中ZrO2 mol%的增加,载体结构从相对的有序经无序再回到相对的有序.Ce0.4Zr0.6O2样品具有最高的储氧性能,而Ce0.25Zr0.75O2样品具有较高的热稳定性.     

93Nb and 17O NMR chemical shifts of niobiophosphate compounds

Niobiophosphate compounds with a large range of niobium and oxygen environments were studied with (93)Nb and (17)O solid-state NMR. (93)Nb isotropic chemical shift of pure niobate Nb(ONb)(6), pure phosphate Nb(OP)(6) and mixed phosphate-niobate Nb(OP)(x)(ONb)((6-x)) (1相似文献   

Imaging phase separation near the Mott boundary of the correlated organic superconductors kappa-(BEDT-TTF)2X

Electronic phase separation consisting of the metallic and insulating domains with 50-100 microm in diameter is found in the organic Mott system kappa-[(h8-BEDT-TTF)(1-x)(d8-BEDT-TTF)x]2Cu[N(CN)2]Br by means of scanning microregion infrared spectroscopy using the synchrotron radiation. The phase separation appears below the critical end temperature 35-40 K of the first-order Mott transition. The observation of the macroscopic size of the domains indicates a different class of the intrinsic electronic inhomogeneity from the nanoscale one reported in the inorganic Mott systems such as high-Tc copper and manganese oxides.     

Evolution of magnetic properties in the normal spinel solid solution Mg(1-x)Cu(x)Cr2O4

We examine the evolution of magnetic properties in the normal spinel oxides Mg(1-x)Cu(x)Cr2O4 using magnetization and heat capacity measurements. The end-member compounds of the solid solution series have been studied in some detail because of their very interesting magnetic behavior. MgCr2O4 is a highly frustrated system that undergoes a first-order structural transition at its antiferromagnetic ordering temperature. CuCr2O4 is tetragonal at room temperature as a result of Jahn-Teller active tetrahedral Cu2+ and undergoes a magnetic transition at 135 K. Substitution of magnetic cations for diamagnetic Mg2+ on the tetrahedral A site in the compositional series Mg(1-x)Cu(x)Cr2O4 dramatically affects magnetic behavior. In the composition range 0 ≤ x ≤ ≈0.3, the compounds are antiferromagnetic. A sharp peak observed at 12.5 K in the heat capacity of MgCr2O4 corresponding to a magnetically driven first-order structural transition is suppressed even for small x. Uncompensated magnetism--with open magnetization loops--develops for samples in the x range ≈0.43 ≤ x ≤ 1. Multiple magnetic ordering temperatures and large coercive fields emerge in the intermediate composition range 0.43 ≤ x ≤ 0.47. The Néel temperature increases with increasing x across the series while the value of the Curie-Weiss Θ(CW) decreases. A magnetic temperature-composition phase diagram of the solid solution series is presented.     

Epitaxial growth and band alignment of (Gd(x)La(1-x))(2)O(3) films on n-GaAs (001)

Herein we demonstrate the epitaxial stabilization of single-crystalline (Gd(x)La(1-x))(2)O(3) films on n-GaAs (001) with a controlled lattice match. (Gd(x)La(1-x))(2)O(3) films have an in-plane epitaxial relationship with a twofold rotation on GaAs (001). Spectroscopic characterization by photoemission and absorption confirms that the band gap of (Gd(x)La(1-x))(2)O(3) film is approximately approximately 5.8eV. However, the conduction band offset is increased by the unpinned Fermi level of the n-GaAs in the (Gd(x)La(1-x))(2)O(3) film (x=0.97). The correlation of the crystalline property and the interfacial band offset by the electrical properties, as probed by capacitance and leakage current measurements, is also discussed.     

The position dependent 15N enrichment of nitrous oxide in the stratosphere.

The position dependent 15N fractionation of nitrous oxide (N2O), which cannot be obtained from mass spectrometric analysis on molecular N2O itself, can be determined with high precision using isotope ratio mass spectrometry on the NO+ fragment that is formed on electron impact in the source of an isotope ratio mass spectrometer. Laboratory UV photolysis experiments show that strong position dependent 15N fractionations occur in the photolysis of N2O in the stratosphere, its major atmospheric sink. Measurements on the isotopic composition of stratospheric N2O indeed confirm the presence of strong isotope enrichments, in particular the difference in the fractionation constants for 15N14NO and 14N15NO. The absolute magnitudes of the fractionation constants found in the stratosphere are much smaller, however, than those found in the lab experiments, demonstrating the importance of dynamical and also additional chemical processes like the reaction of N2O with O(1D).     

The influence of magnetic sublattice dilution on magnetic order in CeNiGe3 and UNiSi2

Polycrystalline samples of the Y-diluted antiferromagnet CeNiGe(3) (T(N)?=?5.5?K) and Th-diluted ferromagnet UNiSi(2) (T(C)?=?95?K) were studied by means of x-ray powder diffraction, magnetization and specific heat measurements performed in a wide temperature range. The lattice parameters of the Ce(1-x)Y(x)NiGe(3) alloys decrease linearly with increasing Y content, while the unit cell volume of U(1-x)Th(x)NiSi(2) increases linearly with increasing Th content. The ordering temperatures of the systems decrease monotonically with increasing x down to about 1.2?K in Ce(0.4)Y(0.6)NiGe(3) and 26?K in U(0.3)Th(0.7)NiSi(2), forming a dome of long-range magnetic order on their magnetic phase diagrams. The suppression of the magnetic order is associated with distinct broadening of the anomalies at T(N,C) due to crystallographic disorder being a consequence of the alloying. Below the magnetic percolation threshold x(c) of about 0.68 and 0.75 in the Ce- and U-based alloys, respectively, the long-range magnetic order smoothly evolves into a short-range one, forming a tail on the magnetic phase diagrams. The observed behaviour of Ce(1-x)Y(x)NiGe(3) and U(1-x)Th(x)NiSi(2) is characteristic of diluted magnetic alloys.