Structure of water in mesoporous organosilica by calorimetry and inelastic neutron scattering

In this paper, we describe the preparation of mesoporous organosilica samples with hydrophilic or hydrophobic organic functionality inside the silica channel. We synthesized mesoporous organosilica of identical pore sizes based on two different organic surface functionality namely hydrophobic (based on octyltriethoxysilane OTES) and hydrophilic (3-aminopropyltriethoxysilane ATES) and MCM-41 was used as a reference system. The structure of water/ice in those porous silica samples have been investigated over a range temperatures by differential scanning calorimetry (DSC) and inelastic neutron scattering (INS). INS study revealed that water confined in hydrophobic mesoporous organosilica shows vibrational behavior strongly different than bulk water. It consists of two states: water with strong and weak hydrogen bonds (with ratio 1:2.65, respectively), compared to ice-Ih. The corresponding O-O distances in these water states are 2.67 and 2.87 ?, which strongly differ compared to ice-Ih (2.76 ?). INS spectra for water in hydrophilic mesoporous organosilica ATES show behavior similar to bulk water, but with greater degree of disorder.     

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.     

The structure factor for liquid nitrogen and liquid oxygen by neutron scattering

The structure factor S(Q) has been measured for liquid nitrogen at 77 K by neutron diffraction at four wavelengths. The effects of Placzek corrections on the self [1, 2] and interference [3] components of the observed differential scattering cross-sections at 0·35, 0·7, 0·84 and 1·06 Å [4] have been investigated. Effective molecular masses and internuclear bond lengths have been obtained by fitting a modified Placzek model to the observed data. It is concluded that after correction the different structure factors agree satisfactorily within the statistical errors of the measurements and the internuclear bond length is close to that measured in the gas phase.     

Structure of liquid iron at pressures up to 58 GPa

We report structural data on liquid iron at pressures up to 58 GPa measured by x-ray scattering in a laser heated diamond anvil cell. The determined structure factor preserves essentially the same shape along the melting curve. Our data demonstrate that liquid iron at high pressures is a close-packed hard-sphere liquid. The results place important constraints on the thermodynamic and transport properties of liquid iron and the melting curve of iron.     

A new high P-T cell for neutron diffraction up to 7 GPa and 2000 K with measurement of temperature by neutron radiography

Abstract

This paper reports developments to enable neutron diffraction at simultaneous high temperatures and pressures using the Paris-Edinburgh cell. These include a new design of a cell assembly with internal heating. One of the novel features of our system is the use of neutron radiographic methods for measurement of temperature. Fully refinable neutron diffraction patterns obtained by time of flight technique with our apparatus are found to be of comparable quality to previous high-pressure studies at ambient temperatures. In this paper we describe the procedures for the generation and measurement of pressure and temperature and illustrate the quality of the data which can be obtained. The present system may be used on a routine basis for experiments up to 7 GPa and temperature approaching 2000 K. Current attempts are discussed for extending these measurements to a wider domain of pressures and temperatures.     

Solidification of selenium melt under pressure up to 6.5 GPa

Abstract

High purity selenium samples were melted under high pressure (≤6.4 GPa) and quenched at various rates ranging from 2 K s^?1 to 500 K s^?1 and the recovered material was examined by X-ray diffraction and electron microscopy. In the entire range of pressure and cooling rate, the melt was found to solidify into a polycrystalline aggregate of the trigonal phase of selenium. The samples obtained by slow cooling of the melt at 6.4 GPa contain, in addition to crystalline phase, regions which appear to be amorphous.     

Molecular motions in liquid ethane studied by cold neutron scattering

In a previous work we report a comparative study of the molecular motions in gaseous and liquid methane and argon. In the present work we present the results of a study of the molecular motions in liquid ethane at three widely different temperatures. The aim is to study the rotational-translational motions of the rigid molecule. The unknown scattering from the librational and other motions of the CH₃ group is experimentally determined from a high-temperature run by a procedure of isolation of this scattering by use of successive approximations in which also the corrections for multiple scattering are involved.It is found that the translational motions are very nearly described by a cross section based on simple Langevin diffusion. The effects of encaging in ethane well below the critical point seem to influence the cross section only rather modestly. The scaling of the “encaging part” of the translational motion from liquid argon to ethane by use of the law of corresponding states is not successful. The rotational motions are equally well described by the Langevin rotational-diffusion model or by the step model. It is observed that certain degrees of rotational freedom tend to be frozen when the freezing point is approached.     

Synchrotron infrared measurements of dense hydrogen to 360 GPa

Diamond-anvil-cell techniques have been developed to confine and measure hydrogen samples under static conditions to pressures above 300 GPa from 12 to 300 K using synchrotron infrared and optical absorption techniques. A decreasing absorption threshold in the visible spectrum is observed, but the material remains transparent at photon energies down to 0.1 eV at pressures to 360 GPa over a broad temperature range. The persistence of the strong infrared absorption of the vibron characteristic of phase III indicates the stability of the paired state of hydrogen. There is no evidence for the predicted metallic state over these conditions, in contrast to recent reports, but electronic properties consistent with semimetallic behavior are observed.     

Dynamics of liquid ammonia from cold neutron scattering

The scattering of 4.1 Å neutrons by liquid ammonia has been measured at 218 K in the angular range of 30–90° using the Trombay rotating crystal spectrometer. The experimental data, after correcting for multiple scattering, have been compared with model calculations, and it is shown that it is possible to get detailed information about the rotational correlation function on the basis of neutron experiments alone. The model assumes Langevin diffusion for translational motions. Rotational motions are described by means of an orientational correlation function which has a gaseous behaviour for times up toτ ₀ and then changes over to a diffusive character with a rotational diffusion constantD _r. Within the framework of the model the correlation function can be described withD _r=0.28×10¹³sec^?1 andτ ₀=0.57×10^?18sec. Corrections for multiple scattering and their dependence on model parameters are discussed.     

Slow neutron scattering and intermolecular excitations in liquid hydrogen

A simple analytical model for inelastic neutron scattering in liquid hydrogen with the effects of delayed diffusion and intermolecular vibrations with a single frequency parameter is proposed. Calculated results show good agreements with experimental results of total and differential scattering cross sections as well as the energy spectra of neutrons in liquid hydrogen moderators, and thus indicate the importance of the consideration of intermolecular excitations in the dynamics of liquid hydrogen.     

Dynamics of supercooled confined water measured by deep inelastic neutron scattering

In this paper, we present the results of deep inelastic neutron scattering (DINS) measurements on supercooled water confined within the pores (average pore diameter ~ 20 Å) of a disordered hydrophilic silica matrix obtained through hydrolysis and polycondensation of the alkoxide precursor Tetra-Methyl-Ortho-Silicate via the sol-gel method. Experiments were performed at two temperatures (250 K and 210 K, i.e., before and after the putative liquid–liquid transition of supercooled confined water) on a “wet” sample with hydration h ~ 40% w/w, which is high enough to have water-filled pores but low enough to avoid water crystallization. A virtually “dry” sample at h ~ 7% was also investigated to measure the contribution of the silica matrix to the neutron scattering signal. As is well known, DINS measurements allow the determination of the mean kinetic energy and the momentum distribution of the hydrogen atoms in the system and therefore, allow researchers to probe the local structure of supercooled confined water. The main result obtained is that at 210 K the hydrogen mean kinetic energy is equal or even slightly higher than at 250 K. This is at odds with the predictions of a semiempirical harmonic model recently proposed to describe the temperature dependence of the kinetic energy of hydrogen in water. This is a new and very interesting result, which suggests that at 210 K, the water hydrogens experience a stiffer intermolecular potential than at 250 K. This is in agreement with the liquid–liquid transition hypothesis.     

Diffraction limit of the theory of multiple small-angle neutron scattering by a dense system of scatterers

Multiple small-angle neutron scattering by a high-density system of inhomogeneities has been considered. A combined approach to the analysis of multiple small-angle neutron scattering has been proposed on the basis of the synthesis of the Zernike–Prince and Moliére formulas. This approach has been compared to the existing multiple small-angle neutron scattering theory based on the eikonal approximation. This comparison has shown that the results in the diffraction limit coincide, whereas differences exist in the refraction limit because the latter theory includes correlations between successive scattering events. It has been shown analytically that the existence of correlations in the spatial position of scatterers results in an increase in the number of unscattered neutrons. Thus, the narrowing of spectra of multiple small-angle neutron scattering observed experimentally and in numerical simulation has been explained.     

Structure and correlation in liquid alloys by X-ray and neutron diffraction

A method for obtaining information about correlation in a liquid or amorphous alloy is presented. The explicit structure in a binary could in principle be determined from three independent diffraction patterns. It is relatively much simpler to measure and analyse the x-ray and neutron intensity patterns and with these alone obtain considerable correlation information, even if more than two atom types are present, by calculating the ratio of the two experimental radial distributions. For the binary the relevance of the ratio derives from the fact that each distribution is a sum of the radial distributions of the three types of atom-pairs, each term being weighted by the appropriate product of scattering amplitudes. The structure of the sample can be analysed by comparing the ratio for any interatomic distance to the values it would have for pure A-A, pure B-B, pure A-B, and random pairing. In a true liquid the results are semiquantitative. In an alloy with well-defined short-range order, the correlation of these close pairings can be clearly determined. Results are shown for liquid NaK and vitreous silica. For any alloy the experimental results would serve to test structural models.     

Investigation of diffusion processes in liquid sodium and sodium-hydrogen melt by quasielastic neutron scattering

The quasielastic neutron scattering experiments on liquid sodium (at T = 378, 573, and 693 K) and sodiumhydrogen melt (T = 693 K, hydrogen concentration ～ 0.4 at %) were performed with the DIN-2PI time-of-flight spectrometer. The characteristics of the diffusion mobility for particles comprising the liquids studied are extracted from the experimental results and analyzed with the help of the phenomenological and “relaxing cage” models. The self-diffusion coefficient in liquid sodium obtained for all temperatures is in the agreement with the values known from literature. The diffusion mobility in pure sodium and in sodium-hydrogen melt were found to be coinciding; it leads to the conclusion that in our experimental conditions hydrogen exists and diffuses in melt in the form of hydride NaH.     

水中受激拉曼散射的能量增强及受激布里渊散射的光学抑制

为提高液体介质中受激拉曼散射的输出能量,提出了通过温度调控来抑制受激布里渊散射的方法,设计了532 nm多纵模宽带脉冲激光泵浦的受激拉曼散射发生系统,测量了不同温度下水中前向受激拉曼散射及后向受激布里渊散射的输出能量,分析了水温、泵浦激光线宽及热散焦效应对受激拉曼散射输出能量影响的物理机制.实验结果表明:通过降低水温可实现对受激布里渊散射过程的有效抑制,同时减小热散焦效应带来的光束畸变,从而有效提高受激拉曼散射的输出能量.研究结果对液体介质中的受激拉曼散射多波长转换具有重要意义.     

The structure factor for liquid nitrogen and liquid oxygen from neutron scattering studies

The structure factor, S(Q), has been measured for liquid nitrogen at 77 K and liquid oxygen at 84 K by neutron diffraction over a range of momentum transfer, Q, from 0·3 to 7·3 Å^-1. In the case of oxygen a correction for magnetic scattering has been included.

The liquid structure factor for nitrogen compares well with that obtained from X-ray diffraction measurements but there are significant discrepancies in the case of oxygen. These may be partially attributed to uncertainty in the form factor for paramagnetic scattering.

The data have been analysed in terms of several different models for the orientational correlation between neighbouring molecules. The results are particularly sensitive to uncertainties in the absolute normalization of the data, the inter-nuclear distance for the molecular structure and Placzek corrections; the effect of these errors is considered in detail. It is shown that some form of orientation correlation must exist but its precise nature could not be obtained from the present data.     

水泥老化过程中水动态的准弹性中子散射(QENS)谱分析

准弹性中子散射(quasi-elastic neutron scattering, QENS)实验是研究水泥老化过程中水动态的一种新颖的实验方法.本文利用老化时间分别为7, 14和30 d水泥样品的QENS谱实验数据, 通过应用四个高斯项的和的能量分辨函数R(Q, E)代替一个高斯项的能量分辨函数来改进经验扩散模型(empirical diffusion model, EDM), 再进行非线性最小二乘拟合.由此导出水泥样品中水动态的相关物理参数: 不动水数密度A, 自由水指数FWI=B₁/(A+B₁+B₂), 洛伦兹函数的半高宽Γ, 移动水跳跃之间的平均停留时间τ ₀及自扩散系数D_t, 而且可得出更为精准的QENS谱拟合曲线.拟合得到的物理参数可定量描述水泥老化过程中水动态过程, 从而为QENS实验在水泥老化过程中水动态研究的应用提供一种合理实用的谱分析方法.     

Thermal neutron diffraction study of liquid carbon disulphide from 165 K to 318 K.

The structure factor of liquid carbon disulphide along the coexistence curve is studied at seven temperatures in the range 165 to 318 K and in a range of the scattering parameter, 9.5<κ[nm^?1]<34. The structure of the liquid over the entire range of states can be described well by the RISM with σ_S=0.33 nm and σ_C=0.34 nm. These values are in agreement with those reported by the majority of other authors. The intermolecular scattering functions are tabulated in this paper.     

Pressure-induced change of the interlayer exchange interaction from ferromagnetic to antiferromagnetic in CS2CuF4 observed by neutron scattering experiments up to 2 GPa

Abstract

Neutron scattering experiments on the two-dimensional Heisenberg ferromagnets Cs₂ CuF₄ and K₂CuF₄ have been performed around 2 ～ 3 GPa over 1·4–15 K. At ambient pressure both the intralayer and the interlayer exchange interactions in these two compounds are ferromagnetic. At about 2 GPa, the interlayer exchange coupling in Cs₂ CuF₄ is found to change from ferromagnetic to antiferromagnetic, while the ferromagnetic intralayer exchange interaction is maintained. Contrary to Cs₂CuF₄, the ferromagnetism in K₂Cuf₄ is not destroyed by pressure up to 9 GPa, that was confirmed in the early study of the magnetic susceptibility measurements.