In-situ EXAFS study on the thermal decomposition of TiH_2

Thermal decomposition behaviors of TiH_2 powder under a flowing helium atmosphere and in a low vacuum condition have been studied using an in situ EXAFS technique.By an EXAFS analysis containing the multiple scattering paths including H atoms,the changes of the hydrogen stoichiometric ratio and the phase transformation sequence are obtained.The results demonstrate that the initial decomposition temperature is dependent on experimental conditions,which occurs,respectively,at about 300 and 400℃ in a low vacuum condition and under a flowing helium atmosphere.During the decomposition process of TiH_2 in a low vacuum condition,the sample experiences a phase change process:δ(TiH_2)→δ(TiH_x)→δ(TiH_1)+β(TiH_x)→δ(TiH_x)+β(TiH_x)+α(Ti)→β(TiH_x)+α(Ti)→α(Ti)+β(Ti).This study offers a way to detect the structural information of hydrogen.A detailed discussion about the decomposition process of TiH_2 is given in this paper.     

充氢镍箔放氢过程的XRD与EXAFS研究

本文通过带有EXAFS附件的X射线衍射仪在实验室用XRD和EXAFS两种方法完成了对充氢镍箔放氢过程的研究,测定了放氢过程中样品中NiH相含量随释氢时间的变化,XRD和EXAFS的结果是一致的,均呈指数规律下降。实验还确定了NiH相中镍和氢的原子比,说明了氢在点阵中的位置,证明实验室EXAFS装置适合这类问题的研究。 关键词：     

X‐ray‐Raman‐scattering‐based EXAFS beyond the dipole limit

X‐ray Raman scattering (XRS) provides a bulk‐sensitive method of measuring the extended X‐ray absorption fine structure (EXAFS) of soft X‐ray absorption edges. Accurate measurements and data analysis procedures for the determination of XRS‐EXAFS of polycrystalline diamond are described. The contributions of various angular‐momentum components beyond the dipole limit to the atomic background and the EXAFS oscillations are incorporated using self‐consistent real‐space multiple‐scattering calculations. The properly extracted XRS‐EXAFS oscillations are in good agreement with calculations and earlier soft X‐ray EXAFS results. It is shown, however, that under certain conditions multiple‐scattering contributions to XRS‐EXAFS deviate from those in standard EXAFS, leading to noticeable changes in the real‐space signal at higher momentum transfers owing to non‐dipole contributions. These results pave the way for the accurate application of XRS‐EXAFS to previously inaccessible light‐element systems.     

Laser Diagnostics of the Mesoscale Heterogeneity of Aqueous Solutions of Polar Organic Compounds

A mesoscale droplet phase, which is spontaneously formed in aqueous solutions of some polar organic compounds, has been experimentally investigated by methods of dynamic light scattering and laser phase microscopy. It is shown that tetrahydrofuran and tert-butanol aqueous solutions demonstrate a strong peak of light scattering intensity in the range of molecular concentrations of about 0.02 to 0.08, which corresponds to inhomogeneities with a characteristic size of about 100 nm. These liquid droplets are enriched with molecules of dissolved substance. A similar light scattering peak for aqueous solutions of glycerol and ethylene glycol is less pronounced. A theoretical model of the phase separation of binary solutions with twinkling (i.e., existing for a finite time) intermolecular hydrogen bonds is developed. The model predicts the existence of an additional low-concentration light scattering peak near the spinodal of the solution free of hydrogen bonds. A characterization of solutions according to the numerical values of twinkling hydrogen bond parameters is outlined.     

EXAFS方法在金属玻璃结构研究中的误差分析

本文对EXAFS方法在金属玻璃结构研究中所得径向距离的误差进行了分析。所做的模拟计算表明当前流行的关于这个问题的误差理论不能圆满地解释这一现象。本文分析了玻璃态和晶态的相移函数,指出在相似的体系中玻璃态和晶态相移函数与k的关系采用线性函数近似时,其斜率可能是不同的,而且无序度相差越大,两者的偏差可能也越大。在EXAFS数据处理过程中,没有考虑这种偏差的影响是造成EXAFS方法结果中径向距离误差的一个原因。本文还提出了一个修正参考样品(晶态)相移函数斜率偏差的方法,并将它应用于Cu₅₅Zr₄₅金属玻璃的EXAFS数据处理中,所得结果与用X射线异常散射方法测定的结果符合得很好。 关键词：     

Muffin‐tin potentials in EXAFS analysis

Muffin‐tin potentials are the standard tool for calculating the potential surface of a cluster of atoms for use in the analysis of extended X‐ray absorption fine‐structure (EXAFS) data. The set of Cartesian coordinates used to define the positions of atoms in the cluster and to calculate the muffin‐tin potentials is commonly also used to enumerate the scattering paths used in the EXAFS data analysis. In this paper, it is shown that these muffin‐tin potentials are sufficiently robust to be used to examine quantitatively contributions to the EXAFS data from scattering geometries not represented in the original cluster.     

相变区硅薄膜拉曼和红外光谱分析

采用等离子体增强化学气相沉积(PECVD)技术制备了一系列不同氢稀释率下的硅薄膜,采用拉曼散射光谱和傅里叶红外光谱技术研究了非晶/微晶相变区硅薄膜的微观结构变化,将次晶结构(paracrystalline structure)引入到非晶/微晶相变区硅薄膜结构中,提出了次晶粒体积分数(f_p),用来表征硅薄膜中程有序程度。结果表明,氢稀释率的提高导致硅薄膜经历了从非晶硅到微晶硅的相变过程,在相变区靠近非晶相的一侧,硅薄膜表现出氢含量高、结构致密和中程有序度高等特性,氢在薄膜的生长中主要起到表面钝化作用。在相变区靠近微晶相的一侧,硅薄膜具有氢含量低、晶化率高和界面体积分数小等特性,揭示了氢的刻蚀作用主控了薄膜生长过程。采用扫描电子显微镜对样品薄膜的表面形貌进行分析,验证了拉曼散射光谱和傅里叶红外光谱的分析结果。非晶/微晶相变区尤其是相变区边缘硅薄膜结构特性优良,在太阳能电池应用中适合用作硅基薄膜电池本征层。     

Peculiarities of the correlation functions, X-ray and neutron scattering in BaTiO3

Based on molecular-dynamics (MD) simulations, we have calculated the static and dynamic correlation functions in a BaTiO₃ crystal. The static correlation functions have been used to study the peculiarities of diffuse scattering in barium titanate showing the experimentally observed anomalous planes. Based on time-dependent pair correlation functions, we have calculated the phonon spectra of BaTiO₃ and studied the central peak of inelastic scattering. The phonon frequencies calculated by the MD method agree well with those obtained previously in the quasi-harmonic approximation. We show that the central peak of inelastic scattering is associated mainly with the soft optic mode and has the same symmetry. The large anisotropy in the displacements of atoms in the soft mode allows the presence of peculiarities in both X-ray scattering and EXAFS spectroscopy to be explained. The characteristic shape of the EXAFS spectra is shown to be explained by the quasi-one-dimensional motion of the oxygen ions in the cubic lattice of BaTiO₃. Our calculation of triple correlation functions shows that the titanium atom in the described model oscillates around the cubic cell center. Explaining the experimental data that have caused disagreement about the nature of the phase transition in BaTiO₃ using the developed model gives grounds to treat the phase transition in barium titanate as a displacive one.     

The effect of self‐consistent potentials on EXAFS analysis

A theory program intended for use with extended X‐ray‐absorption fine structure (EXAFS) spectroscopy and based on the popular FEFF8 is presented. It provides an application programming interface designed to make it easy to integrate high‐quality theory into EXAFS analysis software. This new code is then used to examine the impact of self‐consistent scattering potentials on EXAFS data analysis by methodical testing of theoretical fitting standards against a curated suite of measured EXAFS data. For each data set, the results of a fit are compared using a well characterized structural model and theoretical fitting standards computed both with and without self‐consistent potentials. It is demonstrated that the use of self‐consistent potentials has scant impact on the results of the EXAFS analysis.     

Phase diagrams for semilinear photorefractive coherent oscillator

The sequence of optical phase transitions is considered for a photorefractive coherent oscillator with a conventional mirror and a four-wave mixing phase conjugate mirror. Analogous to phase transitions in solids, the phase diagrams are constructed and defined qualitatively as different states of a whole system (light-induced scattering below the threshold of oscillation, single-frequency oscillation, two-frequency oscillation, and multimode mirrorless oscillation). The attempt of experimental mapping of a phase diagram is presented for a coherent oscillator with Co-doped BaTiO₃. PACS 42.65.Hw; 05.45.-a; 42.65.Pc; 42.65.Sf.     

天然和人工时效Cu55Zr45金属玻璃结构弛豫的EXAFS研究

本文应用EXAFS结构分析法研究了Cu₅₅Zr₄₅金属玻璃经天然和人工时效后引起的结构变化。为了比较,也用EXAFS法测定了淬态样品的结构。与此同时还应用X射线小角散射技术和示差扫描量热仪等观测结构弛豫的手段测量了人工时效样品的相应现象。最后根据观测到的事实提出一个非晶相分离模型来解释这个样品在时效时产生的EXAFS及其傅里叶变换的变化,得到圆满结果。 关键词：     

An investigation of the use of the Hedin-Lundqvist exchange and correlation potential in EXAFS data analysis

In real systems, inelastic processes remove photoelectrons from the elastic scattering channel. This reduces the amplitude of the EXAFS. Traditionally the discrepancies between experimental and theoretical amplitudes were treated by including two semi-empirical reduction factors in the data analysis. Some inelastic effects may, however, be modelled more rigorously using a complex exchange and correlation potential, for example the Hedin-Lundqvist (HL) potential used in most EXAFS data-analysis programs. In this paper a systematic study of the effects of the HL potential on the calculated EXAFS amplitudes is presented. Expressions are derived whereby the EXAFS amplitudes may be examined in the presence of an arbitrary complex potential independently to the rest of the EXAFS signal. These results are used to study the effects of the HL potential on EXAFS data analysis in detail.     

电子衍射条件对Si(111)外延时反射式高能电子衍射强度振荡的影响

本文研究了不同电子衍射条件对Si(111)外延时的反射式高能电子衍射(RHEED)强度振荡的影响,在保持生长条件不变的情况下,沿[112]方位观测时,不同入射角下其强度振荡的相位和初始瞬态响应变化很大,甚至会发生180°相位变化,而在[011]方位观测时,其相位的变化不明显,结合Si(111)面的RHEED强度摇摆曲线测量结果,表明这种与电子衍射条件有关的振荡特性变化,实际上反映了由电子多重散射机理引起的RHEED强度振荡两种情形,对RHEED强度的初始瞬态响应机理也作了探讨。 关键词：     

An X‐ray Raman spectrometer for EXAFS studies on minerals: bent Laue spectrometer with 20 keV X‐rays

An X‐ray Raman spectrometer for studies of local structures in minerals is discussed. Contrary to widely adopted back‐scattering spectrometers using ≤10 keV X‐rays, a spectrometer utilizing ～20 keV X‐rays and a bent Laue analyzer is proposed. The 20 keV photons penetrate mineral samples much more deeply than 10 keV photons, so that high intensity is obtained owing to an enhancement of the scattering volume. Furthermore, a bent Laue analyzer provides a wide band‐pass and a high reflectivity, leading to a much enhanced integrated intensity. A prototype spectrometer has been constructed and performance tests carried out. The oxygen K‐edge in SiO₂ glass and crystal (α‐quartz) has been measured with energy resolutions of 4 eV (EXAFS mode) and 1.3 eV (XANES mode). Unlike methods previously adopted, it is proposed to determine the pre‐edge curve based on a theoretical Compton profile and a Monte Carlo multiple‐scattering simulation before extracting EXAFS features. It is shown that the obtained EXAFS features are reproduced fairly well by a cluster model with a minimal set of fitting parameters. The spectrometer and the data processing proposed here are readily applicable to high‐pressure studies.     

Threshold of oscillation in a ring-loop phase conjugator as a second-order optical phase transition

The threshold behavior is studied for a ring-loop coherent oscillator with a photorefractive strontium barium niobate (SBN) sample. A soft onset of oscillation is revealed and critical slowing down is observed in the temporal development of light-induced scattering below the threshold, thus pointing to a similarity with a second-order phase transition. Received: 10 July 2000 / Published online: 20 September 2000     

XANES and EXAFS study of some metal-metalloid glasses

XANES and EXAFS techniques are proving very popular in the study of local environment in disordered systems. Results of such studies in a large number of metal (Fe, Co, Ni, etc)-metalloid (B, Si, C, etc) glasses are reported. Experiments were done with synchrotron radiation as well as an x-ray tube. The values of bond lengths and co-ordination numbers computed from one-electron single scattering Fourier transform method turn out substantially smaller. The values of bondlength determined from the other EXAFS calculation method and the multiple-scattering computation scheme show good agreement. Importance of choice of suitable reference materials for analysis of data is emphasized. The experimental work was done at EXAFS 5.1 Station at Daresbury Laboratory, U.K.     

Structure and proton conduction in CsDSO4

Caesium hydrogen sulphate is one of the most extensively studied superprotonic conductors with hydrogen bonds. A first order phase transition, from the low conductivity to the high conductivity phase, takes place at 414 K. The crystallographic structure of both phases has been established using high-resolution neutron powder diffraction. Quasielastic neutron scattering has provided information about the spatial and temporal characteristics of proton transport. In the present paper we report the results of reverse Monte Carlo modelling of neutron diffraction (total scattering) data which makes it possible to obtain the diffusion pathways for protons. The results are in good agreement with the qualitative model for proton transport proposed previously; in particular we show clearly that the proton motion is highly correlated with the rotation of the sulphate groups. In the low temperature phase we identify a weak correlation between protons and oxygens on the next-nearest-neighbour sulphate group which increases with temperature and probably drives the phase transition.     

Shock waves in polycrystalline iron

The propagation of shock waves through polycrystalline iron is explored by large-scale atomistic simulations. For large enough shock strengths the passage of the wave causes the body-centered-cubic phase to transform into a close-packed phase with most structure being isotropic hexagonal-close-packed (hcp) and, depending on shock strength and grain orientation, some fraction of face-centered-cubic (fcc) structure. The simulated shock Hugoniot is compared to experiments. By calculating the extended x-ray absorption fine structure (EXAFS) directly from the atomic configurations, a comparison to experimental EXAFS measurements of nanosecond-laser shocks shows that the experimental data is consistent with such a phase transformation. However, the atomistically simulated EXAFS spectra also show that an experimental distinction between the hcp or fcc phase is not possible based on the spectra alone.     

Chemically pumped O2(a-X) laser

A theoretical and experimental study was conducted aimed at achieving laser oscillation in the (a-X) electronic transition of oxygen molecules. Although this transition is highly forbidden by rigorous selection rules, it may nevertheless concede stimulated emission, if the population inversion is high enough. The idea is based on a recently developed apparatus, namely, a porous pipe type high-pressure chemical singlet oxygen generator. A numerical model which describes the characteristics of this generator was developed to estimate the population inversion and small-signal gain achievable in a laser cavity using this source. The calculations showed that the small-signal gain ought to be sufficient to achieve laser oscillation. Preliminary experiments were conducted, but lasing was not yet observed. It is shown that the scattering losses caused by water droplet aerosols are mainly responsible for preventing our system from laser oscillation.     

Freezing of glycerol-water mixtures under pressure

We investigated freezing of pure glycerol as well as glycerol-water (GW) mixtures with 3:1 and 3:2 volume fractions as a function of pressure in the 0-10?GPa range by ruby fluorescence spectroscopy and neutron scattering. We find that the glass transition pressure increases from 5.5?GPa for pure glycerol to 6.5?GPa for the 3:1?GW mixture, with unusually small pressure gradients above. For higher water concentrations close to 3:2, phase separation occurs above 2?GPa where most of the water is expelled in the form of ice VII. The results suggest that glycerol is able to effectively hydrogen bond not more than ≈2.5 H(2)O molecules per glycerol, which seems to support conclusions from molecular dynamics simulations. The data indicate that these fluids could become important as pressure transmitting media for neutron scattering in the 0-7?GPa range, including at low temperatures.