晶体范德华半径的70年

对过去70年来发表的稀有气体、非金属元素和金属元素的晶体范德华半径重要数值进行了系统分析和总结.从常用的数值中推荐了最可靠值,并指出有关晶体范德华半径值及其应用中的若干问题,以及有待今后进一步研究的方向.     

无机盐对辛基酚聚氧乙烯醚乙基磺酸钠临界胶束浓度的影响研究

在(25±0.2)℃的实验温度下,通过用表面张力法确定了辛基酚聚氧乙烯醚(10)乙基磺酸钠(OPS)在无机盐氯化物(LiCl,NaCl,KCl,MgCl2,CaCl2,BaCl2,AlCl3,FeCl3和SmCl3)水溶液中的临界胶束浓度(cmc)值,根据cmc值的变化得出无机盐反离子对非离子-阴离子型表面活性剂OPS的cmc值影响规律.实验数据分析表明,虽然非离子-阴离子型表面活性剂OPS分子中增加了一个非离子氧乙烯单元的亲水性基团,但其cmc值和无机盐反离子浓度[M]之间具有与离子型表面活性剂相似的线性关系:lgcmc=-4.242-(0.2980-0.0102Z/r)lg[M]([M]1mol/L),其中Z和r分别为反离子的价态和范德华原子半径的平均值.无机盐对OPS的cmc的影响具有离子型表面活性剂的性质,不具有非离子型或两性表面活性剂的性质.该关系式亦说明了水溶液中非离子-阴离子型表面活性剂OPS的cmc值与无机盐反离子的浓度、价态和范德华原子半径的平均值有关,反离子对胶束的结合度的大小取决于反离子的价态与范德华原子半径平均值的比值.最后就无机盐反离子对OPS的cmc影响机理进行了简要分析.     

晶体化学中的次级键

应用现代实验技术精确测定分子和晶体的微观结构是 2 0世纪自然科学的一项伟大成就。主要基于晶体结构数据归纳出来的 4套半径数据 ,即离子半径、共价半径、金属原子半径和范德华半径构成了结构化学的支柱。人们利用其各自具有的恒定性和加和性研究物质的结构以及结构与性能的关系 ,已经取得了丰硕的成果。　　离子键、共价键和金属键是化学键的极限类型。不同化学键型之间的过渡所形成的相对于极限键型的偏离被称为键型的变异 ,但是化学键与范德华引力是原子间作用力的不同层次。除后者无须电子云重迭因而没有方向性和饱和性外 ,其作用能要…     

全氟萘烷的化学还原与电化学还原

全氟碳化合物 ( PFCs)是分子中与碳原子相连的氢 (官能团中的除外 )全部被氟原子取代的有机氟化合物 .由于氟元素的电负性最大 ,所以 C— F键的键能很大 ( 4 80～ 5 30 k J/mol) ;PFCs与相应的碳氢化合物相比 ,C— F键的键长 ( 0 .1 3nm)与 C— H键的键长 ( 0 .1 nm)接近 ,而且氟原子的范德华半径( 0 .1 5 nm)与氢原子的范德华半径 ( 0 .1 2 nm)也非常接近 ,所以当碳氢化合物中的氢原子被氟原子取代而形成全氟碳化合物后 ,结构上不会发生太大的变化 [1] ;但是全氟碳化合物的物理化学性质与原来碳氢化合物的物理化学性质有显著差异 ,表…     

脂肪胺的脂水分配系数与结构参数的关系

研究了脂肪胺的脂水分配系数实验值与半经验量子化学计算获得的理论计算参数值间的相关关系,结果表明:实验测定值与分子范德华体积及碳氮键长之间有良好的多元线性关系.     

有机和生物晶体固态核磁共振参数的准确预测

理论计算有助于复杂的有机和生物系统光谱的鉴定.对于核磁共振光谱,固体结晶中的化学位移和四极耦合常数(QCC)受到邻近的分子和晶格的氢键和范德华作用较大的影响,从而显示出与气态单体分子不同的NMR参数.因此,在固体晶体NMR参数的理论计算中有必要将氢键和范德华作用这两个因素考虑进来.基于周期性方法,本文采用L-Ala-Gly二肽和硝基苯晶体作为模型体系来考察该方法计算NMR参数的精度.研究结果显示周期结构模型能够将分子间的氢键和范德华作用考虑进来,得到的化学位移和QCC值明显优于传统的单分子模型和超分子模型得到的结果,采用该方法计算的结果能够重现NMR实验结果.     

聚合物流体的范德华凝聚行为

研究了由聚合物的范德华作用导致的凝聚行为. 研究发现, 尽管聚合物同小分子的相行为的形成原因不同(聚合物体系的相行为是由动能、构象熵项和范德华作用能三项相互竞争的结果, 而小分子的相行为是由动能和范德华作用能相互竞争的结果), 但是它们表现出了极为相似的相行为.     

取代芳烃水中溶解度的测定与估算

本文应用线性溶剂化能相关法回归分析了多种有机有机物的溶解度与范德华体积、Ｌｅｗｉｓ酸性及Ｌｅｗｉｓ碱性之间的相关性，结果表明，溶解度与范德华体积、Ｌｅｗｉｓ酸性及碱性之间呈良好的相关性，用这种方法估算的溶解度值与测定吻合得较好。     

Experimental Foundations of Structural Chemistry

本书较全面地汇集结构化学基本数据,应用于物质结构,化学键和结构．性能关联的实际研究,是一本具有手册性的专著。书中系统提供如下数据：原子,自由基,分子和原子簇电离势;元素与化合物的功函数和能带隙;包括范德华分子在内的键能;相变热和单质与化合物晶体的原子化能;各类化合物在不同物态下的键长以及金属,共价,离子和范德华半径的最新数据。还提供了在静态与动态压力下的相变,元素和化合物的状态方程与弹性模量,以及一些纳米晶体材料的特殊性能等丰富资料。     

流体力学半径对估算胶体微球聚集速率常数的影响

胶体粒子聚集速率常数实验值远低于理论值一直是被普遍关注的问题.聚集速率常数的理论推导是基于粒子的几何半径来考虑的,但决定粒子扩散速率及聚集速率的应该是粒子的流体力学半径(大于几何半径),因而它是使聚集速率常数实验值低于理论值的因素之一.影响流体力学半径的因素很多,其中,带电粒子在溶液中因表面存在双电层,会明显增大流体力学半径,造成聚集速率减慢.而双电层的厚度又随溶液中离子强度的不同而改变.本工作在聚集速率的公式中引入了修正因子,即几何半径与其流体力学半径之比,以修正由于用几何半径代替流体力学半径带来的误差.其中几何半径和流体力学半径可以分别用扫描电镜(SEM)和动态光散射(DLS)来测定.以两种粒径的聚苯乙烯带电微球为例,考察了在不同离子强度下,该误差的大小.结果发现,对于半径为30 nm的微球,用流体力学半径计算的慢聚集速率常数比理论值偏低约8%.该误差随离子强度增加而减少.对于快聚集情况,流体力学半径对聚集速率基本没有影响.     

Van der Waals radii of elements from the data of structural inorganic chemistry

Van der Waals radii of elements were determined from the data of the structural inorganic chemistry: from intersitial distances in CdX₂- and graphite-type structures, bond lengths in van der Waals molecules, molar volumes of A₂-type substances, refractometry data, and from quantum chemical and correlation ratios. The recommended values of van der Waals radii of elements are tabulated.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 24–29, January, 1995.The author is grateful to the administration of the Department of Chemistry at the University of Durham (Great Britain) for the opportunity to perform this work and to Prof. J. Howard and Prof. K. Wade for useful discussions.     

原子的边界半径

本文建议和讨论2了原子大小的一种新量度-原子的边界半径, 经出了边界半径的周期表。对于惰性气体原子和汞原子, 有实验测得的有效半径, 它们与边界半径符合得相当好。原子的边界半径与实验的van der Waals半径有良好的线性关系。因此, 由边界半径可以预言某些原子的有效半径以及van der Waals半径。     

Anisotropy of Atomic Van der Waals Radii in the Gas-Phase and Condensed Molecules\sp{1}

The anisotropic components of van der Waals radii for 5b, 6b and 7b Group elements were determined from the structures of gaseous van der Waals complexes and of crystalline molecular solids. The transition from the gaseous to the solid state reduces the anisotropy of a van der Waals atomic shape. This anisotropy is largely responsible for the changes of intermolecular distances, which are often misinterpreted as an effect of hydrogen bonds.     

Different van der Waals radii for organic and inorganic halogen atoms: a significant improvement in IMOMM performance

The discrepancies between X-ray and integrated molecular orbital molecular mechanics computed geometries for Os(H)₂Cl₂(PⁱPr₃)₂ and Ir(H)₂Cl(P^tBu₂ Ph)₂ are explained by the inadequacy of the default molecular mechanics van der Waals radii for halogen elements. A simple procedure is proposed for the calculation of corrected van der Waals radii, and the application of the corrected radius for chloride is shown to improve substantially the results for the systems under test. Received: 25 February 1997 / Accepted: 7 April 1997     

Anisotropy of the van der Waals Configuration of Atoms in Complex,Condensed, and Gas-Phase Molecules

Anisotropic van der Waals (vdW) radii of 5b–7bsubgroup elements were determined from structures of gas-phase van der Waals complexes and crystal molecular compounds. The anisotropy of the van der Waals configuration of atoms was shown to decrease when going from isolated molecules to the condensed state. Variations in intermolecular distances, which are usually explained in terms of the formation of hydrogen bonds, are substantially governed by the anisotropic effect.     

Atomic and Ionic Radii of Elements 1–96

Atomic and cationic radii have been calculated for the first 96 elements, together with selected anionic radii. The metric adopted is the average distance from the nucleus where the electron density falls to 0.001 electrons per bohr³, following earlier work by Boyd. Our radii are derived using relativistic all‐electron density functional theory calculations, close to the basis set limit. They offer a systematic quantitative measure of the sizes of non‐interacting atoms, commonly invoked in the rationalization of chemical bonding, structure, and different properties. Remarkably, the atomic radii as defined in this way correlate well with van der Waals radii derived from crystal structures. A rationalization for trends and exceptions in those correlations is provided.     

The structure of phosphacymantrene

Proton NMR spectra of phosphacymantrene (π-phospholyl manganese tricarbonyl) orientated in the nematic phases of liquid crystals have been investigated. The derived H-H and H-P direct dipolar coupling constants have been used to determine the relative proton-proton and proton-phosphorus distances. A comparison of the geometrical data of various 5-membered aromatic heterocycles shows that the relative distances between the protons closest to the heteroatom increase with the van der Waals radius of the heteroatom. The results suggest that NMR spectroscopy of orientated molecules can be used to determine van der Waals radii.     

Self‐Assembly of Iodine in Superfluid Helium Droplets: Halogen Bonds and Nanocrystals

We present evidence of halogen bond in iodine clusters formed in superfluid helium droplets based on results from electron diffraction. Iodine crystals are known to form layered structures with intralayer halogen bonds, with interatomic distances shorter than the sum of the van der Waals radii of the two neighboring atoms. The diffraction profile of dimer dominated clusters embedded in helium droplets reveals an interatomic distance of 3.65 Å, much closer to the value of 3.5 Å in iodine crystals than to the van der Waals distance of 4.3 Å. The profile from larger iodine clusters deviates from a single layer structure; instead, a bi‐layer structure qualitatively fits the experimental data. This work highlights the possibility of small halogen bonded iodine clusters, albeit in a perhaps limited environment of superfluid helium droplets. The role of superfluid helium in guiding the trapped molecules into local potential minima awaits further investigation.