X射线衍射进展简介

100年前,劳厄等证明X射线对硫酸铜晶体具有衍射能力,揭开了X射线衍射分析晶体结构的序幕.100年的发展,X射线衍射已经成为自然科学乃至医学、考古、历史学等众多学科发展的必备技术.文章介绍了X射线衍射现象的发现历史,X射线运动学和动力学理论的发展概况,并举例说明了X射线衍射在粉末多晶体、单晶体和人工功能晶体以及人工薄膜材料中的具体应用情况,最后简要展望了X射线衍射技术的发展前景.     

X射线衍射的发现

简单介绍了埃瓦尔德(Ewald P P)、劳厄(von Laue M)和布拉格父子(Bragg W H及Bragg W L)在1912年发现X射线衍射方面的贡献．1911年埃瓦尔德在索末菲的指导下在慕尼黑大学从事博士论文研究，劳厄在与他的讨论中了解到晶格的平移周期与X射线的波长属于同一量级，因此想到在二维光栅的两个衍射方程组中再加一个类似的方程，就可以描述X射线在三维晶体中的衍射．在此假设的指导下，Friedrieh W和Knipping P在1912年4月开始用CuSO4后来用闪锌矿(立方ZnS)进行实验，很快就得到X射线衍射的证据．这不但证明了X射线的波动性，还确定了晶体的三维周期性．老布拉格在1912年夏得知这个消息，与他儿子小布拉格一道尝试用X射线的粒子性解释它，并由小布拉格在剑桥大学重复这个实验．根据衍射斑点的椭圆形状和从Pope与Below那里学到的晶格理论(由此得知ZnS具有面心立方晶格)，小布拉格将X射线在晶体中的衍射看作是X射线从一些晶格平面的反射，从而推导出著名的布拉格方程．布拉格父子开拓了X射线晶体结构分析这门新兴学科，从简单的无机化合物和矿物，逐渐发展到有机化合物和生物大分子．劳厄和布拉格父子分别强调慕尼黑和剑桥的优良科学环境对发现X射线衍射的重要性．鉴于埃瓦尔德在发现X射线衍射的作用及他后来在倒易格子及动力学衍射理论方面的贡献，不少晶体学家认为他也应获得诺贝尔物理奖．     

X射线和中子衍射研究进展

本文概述了近年来X射线和中子衍射方面的研究进展。最重要的进展是在生命科学和材料科学方面。同步辐射的应用大大推动了X射线衍射研究的发展，并由此出现了一系列新的研究领域。中子衍射在工业应用和基础研究方面均获得重要进展。在单晶和多晶的结构分析、数据处理及 晶体对称性研究方面也有突破性成果。     

纪念劳厄发现射线衍射周年

100年前,德国人劳厄发现X射线通过晶体时可以发生衍射效应.随后,英国的布拉格父子等人发展出一系列实验和分析方法,利用X射线晶体衍射解析出具有原子分辨率的分子结构.在过去的100年中,X射线衍射分析对世界的科学发展乃至人们的生活都产生了至关重要的影响,并且在这100年间,X射线衍射实验方法和分析方法也有了长足进步.硬X射线自由电子激光的出现为X射线衍射分析进一步发展提供了更广阔的空间,可以预期,基于自由电子激光的X射线衍射分析会进一步在物理、化学、生物等学科中发挥更为重要的影响.     

时间分辨的X射线衍射

详细论述了时间分辨X射线衍射探测原子动态过程和生物大分子瞬态结构的各种方法。介绍了多种超快X射线脉冲光源及其在材料和生化领域中的研究进展状况。材料方面:在皮秒时间尺度探测到了晶格间距毫埃的微小变化;在亚皮秒的时间尺度直接观测到晶体的超快熔化过程和晶体内的相干声子散射;生物化学方面:采用时间分辨X射线劳厄衍射方法探测了蛋白质大分子结构的变化和功能之间的关系;精确描述了有机分子在光作用下形态发生改变时分子键角的扭转角度,从结构上揭示了其动态机理。     

时间分辨的X射线衍射

详细论述了时间分辨X射线衍射探测原子动态过程和生物大分子瞬态结构的各种方法。介绍了多种超快X射线脉冲光源及其在材料和生化领域中的研究进展状况。材料方面:在皮秒时间尺度探测到了晶格间距毫埃的微小变化;在亚皮秒的时间尺度直接观测到晶体的超快熔化过程和晶体内的相干声子散射;生物化学方面:采用时间分辨X射线劳厄衍射方法探测了蛋白质大分子结构的变化和功能之间的关系;精确描述了有机分子在光作用下形态发生改变时分子键角的扭转角度,从结构上揭示了其动态机理。     

纪念劳厄发现X射线衍射100周年

100年前,德国人劳厄发现X射线通过晶体时可以发生衍射效应．随后,英国的布拉格父子等人发展出一系列实验和分析方法,利用X射线晶体衍射解析出具有原子分辨率的分子结构．在过去的100年中,X射线衍射分析对世界的科学发展乃至人们的生活都产生了至关重要的影响,并且在这100年间,X射线衍射实验方法和分析方法也有了长足进步．硬X射线自由电子激光的出现为X射线衍射分析进一步发展提供了更广阔的空间,可以预期,基于自由电子激光的X射线衍射分析会进一步在物理、化学、生物等学科中发挥更为重要的影响．     

高分辨X射线衍射研究杂质对晶体结构完整性的影响

用水溶液生长晶体的方法生长出了不同掺杂的Sr(NO₃)₂晶体.用电子探针研究了杂质在晶体中的分布情况.结果表明,杂质在晶体中存在扇形分凝,其中Ba在{100}扇形区的含量大于{111}扇形区,而Pb的分凝情况相反,在{111}扇形区的含量大于{100}扇形区.用高分辨X射线衍射摇摆曲线技术研究了纯的、掺Ba的和掺Pb的Sr(NO₃)₂晶体的完整性情况,并用X射线衍射动力学理论计算了完整Sr(NO₃ 关键词： 高分辨X射线衍射 杂质 水溶液晶体生长     

X射线衍射貌相术简介

一、引 言 X射线衍射貌相术(简称X射线貌相术)是利用X射线在晶体中衍射的动力学及运动学衍衬原理,根据晶体中完整及非完整部分衍射的衬度变化及消光规律,来检查晶体材料及器件表面和内部微观结构缺陷的一种方法.随着半导体、激光等科学技术的发展和近完整晶体材料的大量使用,自五十年代末期以来,X射线貌相术的实验和理论有了很大发展,逐渐形成为一种有效的检验手段和一门分支学科[1-3]. X射线貌相术具有下列一些主要优点: 1.用这种方法检查晶体或器件中的缺陷时,通常对样品本身以及其中所含的缺陷状态均具有完全的非破坏性,样品检查后可以…     

晶体X射线衍射的发现及其深远影响

1912年4月,弗里德里希、克里平和劳厄成功地观察到X射线透过硫酸铜晶体后的衍射斑点!随后劳厄推导出描述晶体衍射的著名劳厄方程.由于晶体X射线衍射的发现,劳厄于1914年荣获诺贝尔物理学奖.1912年10月,W.L.布拉格通过X射线透射ZnS晶体实验,推导出了著名的布拉格方程.1915年布拉格父子荣获诺贝尔物理学奖.晶体X射线衍射的发现对自然科学的影响是深远的.2012年是劳厄发现晶体X射线衍射100年,文章回忆了这段光辉的历史及其对科学技术所产生的深远影响,以怀念科学先驱们对科学技术的贡献,弘扬他们对科学研究的认真严谨的科学态度、勇于创新的科学精神和谦逊无私的品德.     

Effect of the Temperature Gradient on the X-ray Diffraction Spectrum of a Quartz Crystal

The spectra of X-ray diffraction from the reflecting atomic plane (1 0 1? 1) of a quartz single crystal are studied in Laue geometry under the action of temperature gradient on a BDER-KI-11K spectrometer with a resolution of 300 eV on the Am241 line of 17.74 keV. The temperature gradient leads to an increase in the intensity of the diffracted beam depending on the heating temperature. It is shown that the intensity of X-ray diffraction in Laue geometry may increase at a temperature gradient of 250°C/cm by two orders of magnitude in comparison with the uniform temperature state of the crystal. The rocking curve of the reflected beam is obtained at a fixed observation angle of 6° and a specified temperature gradient. It is demonstrated that the intensity of the reflected beam increases with increasing temperature gradient (to a certain value), while the spectral width of the reflection line remains constant and is governed by the energy resolution of the spectrometer. A further growth in the temperature gradient leads to an increase in the spectral width of the reflection line with decreasing intensity of the reflected beam.     

Applications of X-ray Diffraction Methods to Quantitative Chemical Analysis

In the 60 years since its discovery, X-ray diffraction has become established as one of the most important techniques in the study of crystalline materials for fundamental and applied research and for routine analyses. Perusal of the literature in scientific fields such as chemistry, metallurgy, mineralogy, and pharmacology shows applications of X-ray diffraction to such varied subjects a s chemical analysis, crystal structure analysis, imperfections, phase equilibria, particle size and strain (stress), orientation of a single crystal or of grains or components within a polycrystalline substance, and order-disorder.     

Simulation of Reciprocal Space Maps with the Use of Spectral Angular Diagrams in the Triple Crystal X-Ray Diffraction Scheme

An approach to the simulation of reciprocal space maps corresponding to the maps obtained experimentally by the triple crystal X-ray diffractometry (TXD) is proposed. A specific feature of the approach is the use of spectral angular distribution diagrams of X-ray radiation, which allows one to visualize the two-dimensional pattern of the spectral angular “composition” of an X-ray beam after its interaction with each element of the scheme and thus to take into account the contribution of the hardware function of the experimental setup. The algorithms developed allow calculations for a wide class of radiation sources (from an X‑ray tube with any material of the anode to a synchrotron radiation source) and X-ray optical elements (slits, X-ray mirrors of monochromators, and analyzers). The results of simulation are compared with the experimental data for dispersive diffraction geometry, which confirms the adequacy of the proposed approach and its applicability to the simulation of a diffraction pattern corresponding to a real experiment in the triple crystal scheme.     

Crystallography Based on Synchrotron Radiation: Experiments of Russian Users of the ESRF BM01 Diffraction Beam Line

The review deals with studies carried out at the BM01 diffraction beam line of the European Synchrotron Radiation Facility. X-ray diffraction analysis of single-crystal proton conductors demonstrates the possibilities of a precise diffraction experiment in which phase transitions associated with the release of crystallization water and transformation of the network of hydrogen contacts are investigated. Scanning of reciprocal space with the help of a 2D detector enables us to determine the new phase symmetry in a thin-film multiferroic sample based on bismuth ferrite (the given phase is stable only under thin-film conditions). A combination of Bragg and diffusion scattering processes is employed to investigate the interdependence between the structure and dynamics of a crystal lattice and the physical properties of a relaxor material with a perovskite-like structure. The complementarity and synergy of neutron and synchrotron experiments are demonstrated using the combined study of materials from the manganese-silicide group, which has revealed a nontrivial relationship between magnetic and crystallographic chiralities in noncollinear magnets. Although the given review is limited to only a few experiments carried out by Russian scientists at the BM01 beam line, they still illustrate a variety of problems that can be solved using a modern diffraction station where the bending magnet of a third-generation synchrotron is employed as the synchrotron radiation source.     

Dynamical Theory of X-Ray Diffraction for Restricted Beams: III. Analysis of Experimental Data for a Porous Crystal

Using the dynamical theory of X-ray diffraction for restricted beams, we have performed quantitative analysis of the structure of an InP(001) porous crystal layer on the basis of experimental data obtained by high-resolution X-ray diffractometry. The parameters of the porous crystal have been determined by simulating coherent and diffuse scattering. The influence of the instrumental function and dynamical effects on the results of investigation has been demonstrated.     

Studies on the growth,structural, optical and laser damage threshold properties of 4-aminopyridinium p-aminobenzenesulfonate p-ammoniobenzenesulfonate monohydrate crystal

An organic nonlinear optical crystal 4-aminopyridinium 4-aminobenzenesulfonate 4-ammoniobenzenesulfonate monohydrate (4APABS) was grown by slow evaporation solution growth technique. The cell parameters of grown crystal were confirmed by single crystal X-ray diffraction analysis. High resolution X-ray diffraction studies revealed the crystalline perfection of grown crystal. The functional groups present in title compound were confirmed by FTIR spectral studies. UV–vis spectral studies revealed that the grown crystal is transparent in the entire visible region. Single and multiple shots laser induced surface damage threshold values of the grown crystal were measured using Nd:YAG laser. The relative second harmonic generation efficiency of grown crystal was found to be 2.2 times that of KDP crystal.     

X-ray Phase Contrast at Diffraction Focusing of a Spherical Wave in a Short-Period Superlattice

The possibility of reconstructing the internal structure of one-dimensional phase objects at diffraction focusing of X-ray spherical wave was investigated. As a crystal analyzer a strongly absorbing wedge-shaped short period superlattice with a rib parallel to the diffraction vector was used in symmetric Laue geometry case. It is shown that by moving a phase object along the direction of diffraction vector one can bring different satellites in the focusing condition. It is possible to restore an additional wave phase acquired in the phase object by recording the entire map of obtained data.     

Molecular Structure of the Eudesmanolide Septulinolide

The molecular structure of septuplinolide from Calea septuplinerva was determined by single crystal X-ray diffraction analysis. This requires revision of stereochemistry at C4 from 4β-OH to 4α-OH in the septuplinolide molecule. Also, high-field ¹H and ¹³C NMR spectral assignments of the lactone are given.     

X射线衍射增强成像中的定量测量

提出了一种基于X射线衍射增强成像(DEI)断层计算机X射线层析术(CT)图像的物体尺寸精确测量方法.X射线衍射增强成像是一种基于相位衬度的成像技术.通过建立DEI的简化模型,研究衍射成像过程中品体转角、投影图像谷点位置、成像系统等效模糊等因素之间关系,由此具体探讨了系统模糊效应对圆物体边界成像带来的位置偏移,并以圆形被测样品为例.提出可精确测定直径的简单有效算法.通过理论仿真模型数据和北京同步辐射装置上的实测数据验证了该算法的精度.该方法实现了利用DEI图像对被测物体几何尺寸的精确测量,可用于对牛物组织样品等物体内部微小结构的尺寸的精确测量.     

衍射分析用的X射线管谱线纯度的定量测定

本文提出了衍射分析用的X射线管谱线纯度的定量测定方法。在国产衍射仪上用石英单晶作分光晶体进行展谱测定。实验测得的各种波长X射线的强度应还原为X射线管窗口处的出射强度。对影响强度的各种因素作了详细的理论分析,给出了对应于不同靶、不同杂质元素的强度还原换算因子表。X射线管阳极靶元素主特征谱线强度用铜或铝吸收箔进行衰减,以避免计数损失造成的误差。用这一方法,对许多X射线管进行了测定。 关键词：