Density-driven structural transformations in network forming glasses: a high-pressure neutron diffraction study of GeO(2) glass up to 17.5?GPa

The structure of GeO(2) glass was investigated at pressures up to 17.5(5)?GPa using in situ time-of-flight neutron diffraction with a Paris-Edinburgh press employing sintered diamond anvils. A new methodology and data correction procedure were developed, enabling a reliable measurement of structure factors that are largely free from diamond Bragg peaks. Calibration curves, which are important for neutron diffraction work on disordered materials, were constructed for pressure as a function of applied load for both single and double toroid anvil geometries. The diffraction data are compared to new molecular-dynamics simulations made using transferrable interaction potentials that include dipole-polarization effects. The results, when taken together with those from other experimental methods, are consistent with four densification mechanisms. The first, at pressures up to ??5?GPa, is associated with a reorganization of GeO(4) units. The second, extending over the range from ??5 to 10?GPa, corresponds to a regime where GeO(4) units are replaced predominantly by GeO(5) units. In the third, as the pressure increases beyond ～10?GPa, appreciable concentrations of GeO(6) units begin to form and there is a decrease in the rate of change of the intermediate-range order as measured by the pressure dependence of the position of the first sharp diffraction peak. In the fourth, at about 30?GPa, the transformation to a predominantly octahedral glass is achieved and further densification proceeds via compression of the Ge-O bonds. The observed changes in the measured diffraction patterns for GeO(2) occur at similar dimensionless number densities to those found for SiO(2), indicating similar densification mechanisms for both glasses. This implies a regime from about 15 to 24?GPa where SiO(4) units are replaced predominantly by SiO(5) units, and a regime beyond ～24?GPa where appreciable concentrations of SiO(6) units begin to form.     

Glass fragility and atomic ordering on the intermediate and extended range

The relation between the fragility of glass-forming systems, a parameter which describes many of their key physical characteristics, and atomic scale structure is investigated by using neutron diffraction to measure the topological and chemical ordering for germania, or GeO(2), which is an archetypal strong glass former. We find that the ordering for this and other tetrahedral network-forming glasses at distances greater than the nearest neighbor can be rationalized in terms of an interplay between the relative importance of two length scales. One of these is associated with an intermediate range, the other with an extended range and, with increasing glass fragility, it is the extended range ordering which dominates.     

Refinement of hydrogen positions in (NH4)2SeO4

The crystal structure of ammonium selenate has been studied by means of single crystal x-ray and neutron diffraction with the purpose of the refinement of hydrogen positions. The refined hydrogen positions obtained by single crystal neutron diffraction show that N-H bond lengths form a regular tetrahedron in an ammonium ion. The single crystal x-ray diffraction data show that N-H bond lengths are shorter than those obtained by neutron diffraction and are not equal between themselves. Thus, the comparison of the results of x-ray and neutron diffraction allows one to suggest that the shorter N-H bond lengths obtained by x-ray diffraction reflect the distribution of the electron charge density of ammonium ions within the (NH₄)₂SeO₄ crystal lattice. The text was submitted by the authors in English.     

The structure of liquid methanol revisited: a neutron diffraction experiment at −80 °C and +25 °C

Pulsed neutron diffraction with isotope substitution on the hydroxyl hydrogens (H) is used to study the structure of pure liquid methanol at ?80 °C and +25 °C. Although this liquid has been studied with neutrons several times in the past this is the first time that the composite partial structure factors, XX, XH and HH, are derived from the diffraction data. Here X represents a weighted sum of correlations from carbon (C), oxygen (O), and methyl hydrogen (M) atoms on the methanol molecule. The data are used in an empirical potential structure refinement (EPSR) computer simulation of the liquid at both temperatures. Model distributions of molecules consistent with these data are used to estimate the individual site—site radial distribution functions, the coefficients of the spherical harmonic expansion of the orientational pair correlation function, and the length of possible chains of methanol molecules formed in the liquid. Although the results are qualitatively similar to those of earlier computer simulation studies of this liquid, they do differ in detail from previous work. In particular, although most molecules in the liquid are found as part of chains up to 10 molecules long, the average chain length is only about 2.7 molecules at both temperatures, there are about 1.3 hydrogen bonds per molecule on average, and the chains are highly nonlinear on average.     

A neutron and x-ray diffraction investigation of intermediate range structure in silver borate glasses

The ion diffusion mechanism in ion conducting glasses has in many reports been suggested to be linked to the structure. However, in most cases the structures of the glasses are not very well known. We have investigated the structure of the glass system (AgI)_x (Ag₂O-2B₂O₃)_1−x, with x=0, 0.6 by neutron and x-ray diffraction experiments. AgI doping produces an intense peak in the neutron data at an anomalously low Q-value (0.8 Å⁻¹) that indicates increased intermediate range ordering. Only a weak peak is observed at a similar Q-value in the x-ray structure factor. By comparing the different neutron and x-ray weighting factors the origin of the anomalous peak is unambiguously attributed to correlations within the B-O network. The experimental results have been used to model the glasses by Reverse Monte Carlo simulations to obtain more detailed views of the structures. Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11 – 18 Sept. 1994     

Medium-range structural properties of vitreous germania obtained through first-principles analysis of vibrational spectra

We analyze the principal vibrational spectra of vitreous GeO(2) and derive therefrom structural properties referring to length scales beyond the basic tetrahedral unit. We generate a model structure that yields a neutron structure factor in accord with experiment. The inelastic-neutron, the infrared, and the Raman spectra, calculated within a density-functional approach, also agree with respective experimental spectra. The accord for the Raman spectrum supports a Ge-O-Ge angle distribution centered at 135 degrees. The Raman feature X(2) is found to result from vibrations in three-membered rings, and therefore constitutes a distinctive characteristic of the medium-range structure.     

Determination of diffusion profiles in thin film couples by means of x-ray-diffraction

An x-ray method for the determination of concentration profiles in thin film diffusion couples is presented. This method is based on the theory of Fourier analysis of x-ray diffraction profiles which is generalized to polycrystalline samples showing nonuniform lattice parameter. A Fourier synthesis of the concentration spectrum is possible when the influences of the particle size and the strain in the sample as well as the instrumental function are eliminated from the measured diffraction profile. This can be done by means of reference profiles obtained from layers of the diffusion components. Absorption of the radiation in the sample is negligible when diffusion couples of symmetrical sandwich structure are used. The method is tested experimentally in the system Au-Cu.     

Network topology of deeply supercooled water

Empirical potential structure refinements have been made to recent high-energy x-ray diffraction data, providing molecular models of deeply supercooled water. The average O-O coordination number is found to drop from 5.13 at 293?K to 4.85 at 244?K, within 3.5?Å. Triplet O-O-O bond angle distributions reveal a broad peak centred at 96.4° at 293?K which shifts to 100.0° at 244?K, indicative of the local geometry becoming increasingly tetrahedral with decreasing temperature. However, although the number of non-bonded interstitial molecules between the first and second shells is depleted upon cooling, the number of interstitial molecules forming triplets that are embedded within the hydrogen bonded tetrahedral network at θ_OOO?=?53°, remains constant. This is consistent with previous observations of an invariant O-O coordination number with temperature (4.24 out to 3.3?Å) and corresponds to non-bonded molecules positioned at close to half the ideal tetrahedral angle. Both -O-O-O- and hydrogen-bonded -O-H-O- ring length distributions show increases in 6 and 7-membered rings upon supercooling. This is concomitant with a shift and increase in intensity of peaks at r₄ ～8.7?Å and r₅ ～10.8?Å in the oxygen-oxygen pair distribution function, which in the models correspond to correlations between adjacent and next-nearest-neighbour hydrogen-bonded rings.     

非晶态合金Co81.5B18.5结构的研究

本文叙述了用X射线衍射方法及偏振中子衍射方法对Co_81.5B_18.5非晶合金的结构研究。利用两种数据处理方法,从实验结果中计算了Co_81.5B_18.5的偏干涉函数(PSF),S_ij(Q),和偏简约径向分布函数G_ij(r)。并对这两种结果作了比较。最后计算了一种模型简单单元的中子衍射散射强度,并讨论了这一非晶合金的结构模型。 关键词：     

Charge and spin structure factors in random binary alloys

The charge and spin structure factors, that are important in the x-ray and neutron scattering, have been examinated in random binary alloys, in the framework of the Coherent Potential Approximation (CPA). The spin structure factor shows a characteristic feature, due to the disorder, which in transition metal alloys is expected to give a more contracted neutron form factor.     

Spin correlations in the paramagnetic phase and ring exchange in La2CuO4

Spin correlations in the paramagnetic phase of La(2)CuO(4) have been studied using polarized neutron scattering, with two important results. First, the temperature dependence of the characteristic energy scale of the fluctuations and the amplitude of the neutron structure factor are shown to be in quantitative agreement with the predictions of the quantum nonlinear sigma model. Second, a comparison of a high-temperature series expansion of the equal-time spin correlations with the diffuse neutron intensity provides definitive experimental evidence for ring exchange.     

Isotope effects in water as investigated by neutron diffraction and path integral molecular dynamics

The structures of heavy and light water at 300?K were investigated by using a joint approach in which the method of neutron diffraction with oxygen isotope substitution was complemented by path integral molecular dynamics simulations. The diffraction results, which give intra-molecular O-D and O-H bond distances of 0.985(5) and 0.990(5)??, were found to be in best agreement with those obtained by using the flexible anharmonic TTM3-F water model. Both techniques show a difference of ??0.5% between the O-D and O-H intra-molecular bond lengths, and the results support a competing quantum effects model for water in which its structural and dynamical properties are governed by an offset between intra-molecular and inter-molecular quantum contributions. Further consideration of the O-O correlations is needed in order to improve agreement with experiment.     

Total x-ray scattering of spider dragline silk

Total x-ray scattering measurements of spider dragline silk fibers from Nephila clavipes, Argiope aurantia, and Latrodectus hesperus all yield similar structure factors, with only small variations between the different species. Wide-angle x-ray scattering from fibers orientated perpendicular to the beam shows a high degree of anisotropy, and differential pair distribution functions obtained by integrating over wedges of the equatorial and meridian planes indicate that, on average, the majority (95%) of the atom-atom correlations do not extend beyond 1 nm. Futhermore, the atom-atom correlations between 1 and 3 nm are not associated with the most intense diffraction peaks at Q=1-2 ?(-1). Disordered molecular orientations along the fiber axis are consistent with proteins in similar structural arrangements to those in the equatorial plane, which may be associated with the silk's greater flexibility in this direction.     

The correlation of molecular orientation in liquid water by neutron and X-ray scattering

The neutron diffraction structure factor for heavy water at 22°c has been measured for momentum transfers, ?Q, up to a Q of 13 å ^-1. The results have been interpreted by abstracting the molecular structure effects as far as possible and using models for the correlation of orientation of pairs of molecules ranging from completely uncorrelated orientation to that for adjacent molecules in ice I. Neither these nor any of the popular models for the structure of water, nor a non-hydrogen bonded model, fit the neutron diffraction data over the whole range of Q. Nevertheless, information about the molecular-centres structure factor is obtained, especially for Q up to about 3 å ^-1.

The method of analysis is generalized and applied to x-ray diffraction data and in particular to x-ray data for liquid water. It is shown that this method of analysis has some advantages over the conventional one. The effect of correlation of molecular orientation is less than that of molecular structure on x-ray scattering by water and rather more extensive information is obtained for the molecular-centres structure factor than from neutron data—if the conventional assumption of atomic electron clouds is accepted.

A comparison of the x-ray and neutron scattering data for liquid heavy water shows that the two sets of data are reasonably consistent for any of the usual models for water, except for the region of Q between 3 and 5 å ^-1. The molecular-centres structure factor of water has a weak double humped first maximum with peaks at 2·0 å ^-1 and 2·9å ^-1, probably followed by a damped oscillation. This contrasts with atomic liquids but is similar to that found in liquid carbon tetrachloride. The structure of liquid water is not, therefore, necessarily unique or unusual.     

化学气相沉积法制备Zn2GeO4纳米线及其发光性质的研究

利用化学气相沉积法（CVD）,气-液-固（VLS）生长法则在表面溅有金属Au催化剂层的1 cm×1 cm的Si片上制备三元Zn₂GeO₄纳米线。X射线衍射仪（XRD）测试结果表明,锌源与锗源质量比为8：1时可成功制备出Zn₂GeO₄纳米结构;扫描电子显微镜（SEM）测试结果表明,Zn₂GeO₄纳米线直径为100 nm,长度为10~11 μm;光致发光（PL）测试结果表明,Zn₂GeO₄纳米线在432和480 nm处具有两个发光峰,最后对其生长机理进行了分析。     

SrTiO3 displacive transition revisited via coherent X-ray diffraction

We present a coherent x-ray diffraction study of the antiferrodistortive displacive transition of SrTiO3, a prototypical example of a phase transition for which the critical fluctuations exhibit two length scales and two time scales. From the microbeam x-ray coherent diffraction patterns, we show that the broad (short-length scale) and the narrow (long-length scale) components can be spatially disentangled, due to 100-microm-scale spatial variations of the latter. Moreover, both components exhibit a speckle pattern, which is static on a approximately 10 mn time scale. This gives evidence that the narrow component corresponds to static ordered domains. We interpret the speckles in the broad component as due to a very slow dynamical process, corresponding to the well-known central peak seen in inelastic neutron scattering.     

The structure and thermal motion of simple liquids—I

The characteristics of the liquid state are discussed qualitatively in terms or the forces between molecules, and their thermal motion. Experimental methods available for studying structure and thermal motions on a microscopic scale are outlined.

In particular the relation of the static pair distribution function to neutron and x-ray scattering is considered and the general features of the results presented.     

Angular and polarization correlations in the (n, γ) reaction

Parity-odd and parity-even correlations in neutron radiative capture are considered. We discuss the correlation mechanisms, their magnitudes, dependence on neutron energy and averaging over the final nuclear states. The total number of correlations when s- and p-wave neutron capture and E1 and M1 γ-transitions are taken into account, is equal to 17 (8 parity odd and 9 parity even). The correlations in the integrated γ-quantum spectrum are divided into three classes which contain information about different properties of the compound nucleus.     

Structural description of pressure-induced amorphization in ZrW2O8

ZrW2O8 undergoes a high-pressure amorphization transition above 1.5 GPa to a phase which is recoverable to ambient conditions. Reverse Monte Carlo modeling of neutron and x-ray total scattering data from ZrW2O8 recovered from approximately 4 GPa shows that the large increase in density on pressurizing ZrW2O8 is accommodated within the structure by increased bonding between the WO4 tetrahedra. This increases the tungsten coordination; changes to the ZrO6 octahedral environment are not required. This densified crystal-based model, which contains significant local disorder within a distorted periodic structure, is also in reasonable agreement with x-ray and neutron total scattering data measured in situ at high pressure.