四面体结构的固态等价轨道和能态的自旋--轨道耦合双群分类

本文按照Ｃ—Ｃ单键和烃类化学键的性质，根据ＬＣＡＯ—ＭＯ近似法，将原子波函数基转变为四面体分子的酉等价轨道基，并由这一套酉等价基组合出金刚石、ＧａＡｓ这类等电子晶体离域化的基Ｂｌｏｃｈ函数。详细分析了晶体能带结构中简并态的对称性约化分解。给出了自旋一轨道耦合的主要应用．     

Heck偶联反应在有机单分子膜上的应用

利用Heck偶联反应成功地改变了自组装单分子有机薄膜的化学结构以及末端基团,薄膜末端的碘苯基团与对卤苯乙烯在标准的Heck反应条件下成功发生了偶联反应.这些薄膜经过了接触角、膜厚以及X射线光电子能谱的详细表征.这种表面修饰的方法有效地改变有机薄膜的表面化学.     

Adsorption-induced scission of carbon-carbon bonds

Covalent carbon-carbon bonds are hard to break. Their strength is evident in the hardness of diamonds and tensile strength of polymeric fibres; on the single-molecule level, it manifests itself in the need for forces of several nanonewtons to extend and mechanically rupture one bond. Such forces have been generated using extensional flow, ultrasonic irradiation, receding meniscus and by directly stretching a single molecule with nanoprobes. Here we show that simple adsorption of brush-like macromolecules with long side chains on a substrate can induce not only conformational deformations, but also spontaneous rupture of covalent bonds in the macromolecular backbone. We attribute this behaviour to the fact that the attractive interaction between the side chains and the substrate is maximized by the spreading of the side chains, which in turn induces tension along the polymer backbone. Provided the side-chain densities and substrate interaction are sufficiently high, the tension generated will be strong enough to rupture covalent carbon-carbon bonds. We expect similar adsorption-induced backbone scission to occur for all macromolecules with highly branched architectures, such as brushes and dendrimers. This behaviour needs to be considered when designing surface-targeted macromolecules of this type-either to avoid undesired degradation, or to ensure rupture at predetermined macromolecular sites.     

芳香族碳氢化合物等离子体化学反应的研究

本文研究了七种芳香族碳氢化合物的气相IR激光化学,主要是等离子体化学.实验说明.在功率密度I≤13.5GW·CM~(-2)下,它们不能通过红外多光子吸收发生可检测的反应,仅当它们与环境气体混合击穿—成等离子体时,才有明显的反应发生.反应的结果,它们均以乙炔为主要产物,并伴有少量其它小分子碳氢化合物生成.实验还证实了该条件下它们的反应属等离子体下的热反应,并非等离子体辐射引起的光反应,且初始过程中包括单分子最弱键断裂的基元反应.     

Understanding and exploiting C-H bond activation

The selective transformation of ubiquitous but inert C H bonds to other functional groups has far-reaching practical implications, ranging from more efficient strategies for fine chemical synthesis to the replacement of current petrochemical feedstocks by less expensive and more readily available alkanes. The past twenty years have seen many examples of C-H bond activation at transition-metal centres, often under remarkably mild conditions and with high selectivity. Although profitable practical applications have not yet been developed, our understanding of how these organometallic reactions occur, and what their inherent advantages and limitations for practical alkane conversion are, has progressed considerably. In fact, the recent development of promising catalytic systems highlights the potential of organometallic chemistry for useful C-H bond activation strategies that will ultimately allow us to exploit Earth's alkane resources more efficiently and cleanly.     

Hyperconjugation not steric repulsion leads to the staggered structure of ethane

Many molecules can rotate internally around one or more of their bonds so that during a full 360 degrees rotation, they will change between unstable and relatively stable conformations. Ethane is the textbook example of a molecule exhibiting such behaviour: as one of its two methyl (CH3) groups rotates once around the central carbon-carbon bond, the molecule will alternate three times between an unstable eclipsed conformation and the preferred staggered conformation. This structural preference is usually attributed to steric effects; that is, while ethane rotates towards an eclipsed structure, the electrons in C-H bonds on the different C atoms are drawing closer to each other and therefore experience increased repulsion, introducing a rotation barrier that destabilizes the eclipsed structure. Stabilization of the staggered structure through rotation-induced weakening of the central C-C bond and hyperconjugation has been considered to be involved, but evaluation of the contributions of these effects to ethane's internal rotation barrier and conformational preference remains difficult. Here we report a series of ethane structure optimizations, where successive removal of different interactions indicates that ethane's staggered conformation is the result of preferential stabilization through hyperconjugation. Removal of hyperconjugation interactions yields the eclipsed structure as the preferred conformation, whereas repulsive forces, either present or absent, have no influence on the preference for a staggered conformation.     

Formation of thermally stable alkylidene layers on a catalytically active surface

Materials containing organic-inorganic interfaces usually display a combination of molecular and solid-state properties, which are of interest for applications ranging from chemical sensing to microelectronics and catalysis. Thiols--organic compounds carrying a SH group--are widely used to anchor organic layers to gold surfaces, because gold is catalytically sufficiently active to replace relatively weak S-H bonds with Au-S bonds, yet too inert to attack C-C and C-H bonds in the organic layer. But although several methods of functionalizing the surfaces of semiconductors, oxides and metals are known, it remains difficult to attach a wide range of more complex organic species. Organic layers could, in principle, be formed on the surfaces of metals that are capable of inserting into strong bonds, but such surfaces catalyse the decomposition of organic layers at temperatures above 400 to 600 K, through progressive C-H and C-C bond breaking. Here we report that cycloketones adsorbed on molybdenum carbide, a material known to catalyse a variety of hydrocarbon conversion reactions, transform into surface-bound alkylidenes stable to above 900 K. We expect that this chemistry can be used to create a wide range of exceptionally stable organic layers on molybdenum carbide.     

用光电子能谱研究金属锰、镁表面与甲醇、乙醇反应

用XPS和UPS法研究金属Mn、Mg表面与CH_3OH、C_2H_5OH的反应,室温下,ROH(R=CH_3,C_2H_5)以RO~-的形态吸附在Mg表面,Mn表面有较高的活性,ROH除以RO~-的形态被吸附外,部分还分解为O~(2-)和脱附的碳氢化合物,加热至600K时,Mn表面RO~-完全分解为O~(2-)和R,后者与表面氢结合后脱附,部分C_2H_5O~-中的碳成无定形碳并在～675K加氢脱附,ROH在氧化锰表面除以RO~-的形态被吸附外,在高于650K时还产生CH_2O_(a)、C_2H_4O_(a)等,这些物种在700K依然存在,氧化使锰表面断裂R—O和C—C键的活性降低而其脱氢活性仍然存在。     

直接键连C-C键核自旋偶合常数的量子化学计算

利用PM3级别上的最大重迭对称性分子轨道法对26个化合物进行构型优化。结合自然杂化轨道方法和最大键级杂化轨道方法,计算了其杂化轨道,由此拟合出计算C-C键偶合常数的简单关系式,计算了各种烃类分子中不同的C-C键偶合常数,计算值和实验数据较为吻合,为从简单价键理论角度解释和计算1JCC提供了一种简便直观的方法。     

可重图的Randi指标的极值问题

图G的Randi指数,χ（G）,是分子图的一种拓扑指标,它的值可以反映分子的许多物理化学性质.在化学分子中双键是普遍存在的.为此,研究了恰有一条重边的可重图的Randi指标的极值问题,给出了树图及化学树图的Randi指标的极值及相应的结构.     

淀粉分子电子结构的量子化学研究(Ⅰ):结构单元、糖苷键和氢键的特性

运用量子化学计算研究淀粉分子的微观结构和化学键的性质，淀粉分子的反应活性中心为C3位，C2位和C6位羟基，活性顺序为C3位羟基＞C2位羟基＞C6位羟基。糖苷键的成键效应不大，反键效应较明显，糖苷键中C－O键极性大，键级小，氧上带很多电荷。离子性明显，易受亲电试剂（如氢离子）的进攻。     

分子键连接性指数及其应用

基于分子拓扑图的边,即非氢原子间的化学键,提出键参数ti,并在ti的基础上定义分子键连接性指数F.F对有机化合物具有良好的结构选择性,而且与链烷烃、脂肪醇的沸点都具有良好的线性关系, 使用该模型对85个链烷烃和37个脂肪醇的沸点的估算结果接近实验值, 且计算简便,物理意义明确.     

C-H键核自旋偶合常数和伸缩频率的最大键级杂化轨道研究

利用PM3级别上的最大重迭对称性分子轨道法和最大键级杂化轨道方法,计算了系列碳氢化合物的杂化轨道,拟合出了计算C—H键核自旋偶合常数和伸缩频率的简单关系式。研究了各种碳氢化合物中不同的C—H键核自旋偶合常数和伸缩频率。结果表明,碳氢化合物中的C—H核自旋偶合常数和伸缩频率主要取决于碳原子的轨道杂化作用,为从简单价键理论角度解释和计算1JCH和νCH提供了一种简便直观的方法。     

Formation and propagation of matter-wave soliton trains

Attraction between the atoms of a Bose-Einstein condensate renders it unstable to collapse, although a condensate with a limited number of atoms can be stabilized by confinement in an atom trap. However, beyond this number the condensate collapses. Condensates constrained to one-dimensional motion with attractive interactions are predicted to form stable solitons, in which the attractive forces exactly compensate for wave-packet dispersion. Here we report the formation of bright solitons of (7)Li atoms in a quasi-one-dimensional optical trap, by magnetically tuning the interactions in a stable Bose-Einstein condensate from repulsive to attractive. The solitons are set in motion by offsetting the optical potential, and are observed to propagate in the potential for many oscillatory cycles without spreading. We observe a soliton train, containing many solitons; repulsive interactions between neighbouring solitons are inferred from their motion.     

肟和环戊二烯杂Diels-Alder反应的理论计算

应用量子化学中的密度泛函（B3LYP/6-311G(d,p)）和二级微扰（MP2/6-311G(d,p)）方法对肟和环戊二烯的杂Diels-Alder反应机理进行了计算.结果表明,碳氮键先于碳碳键生成,碳氮键和碳碳键的生成与断裂属非同步的协同过程,C=O键在反应中钝化,不参与反应;反应符合前线轨道理论,利于反应进行;从热力学和动力学角度分析,此反应可以进行,优化计算的结果意义较大;反应计算数据与已有实验结果一致.     

简单铁盐催化的Suzuki-Miyaura偶联反应研究

开发一种廉价、无毒的过渡金属用于催化Suzuki-Miyaura偶联反应具有重要的现实意义。本文选取简单的铁盐作为研究对象,考察了不同铁盐、碱以及溶剂对催化Suzuki-Miyaura偶联反应的影响。结果表明:在乙醇溶液中,K2CO3作为碱,5 mol%FeCl2·4H2O在80°C下能够有效催化各种溴代芳烃及碘代芳烃与芳基硼酸的Suzuki-Miyaura偶联反应,产率在33%~99%之间。     

从芳香性碳-碳双键的反应特性阐述碳纳米管功能化修饰

 纳米材料的功能化修饰构成了现代纳米技术的重要组成部分。作为纳米材料的成员之一,碳纳米管不易分散或溶解于任何溶剂。为了改善碳纳米管的分散/溶解性能,对其进行必要的化学修饰是可行的途径。构成碳纳米管的芳香性碳-碳双键是其功能化修饰主体。利用有机化学碳-碳双键反应的基本理论知识,能指导碳纳米管的修饰,并可预测碳纳米管的形貌及电子性能改变规律。而碳纳米管的功能化修饰成果,也有助于增强难溶有机化合物的碳-碳双键反应特性和规律的理论基础。本文从近年的科研成果出发,从结构-性能角度深入探讨了不同修饰方法对碳纳米管形貌及结构的影响。基于碳-碳双键的加成反应有效保持了原始碳纳米管的形貌,更有利于修饰碳纳米管的广泛应用。     

Binding energies and interaction origins between nonclassical single-electron hydrogen,sodium and lithium bonds and neutral boron-containing radicals: a theoretical investigation

Nonclassical single electron hydrogen,sodium and lithium bonds(SEHBs,SENaBs and SELiBs)between single electron acceptors X–A(A=H,Na,Li;X=CN,HCC,HO,NC,CF3)and neutral radicals BY2(Y=H,OH,CH3)and have been systematically investigated by high level theoretical methods,such as second-order Mφller-Plesset perturbation theory(MP2),spin-component-scaled MφllerPlesset theory(SCS-MP2),the coupled cluster method with perturbative triples(CCSD(T)),and the correlation consistent composite approach(ccCA).Binding energies have been corrected for zero-point vibrational effects and(when applicable)basis set superposition error.The quantum theory of atoms in molecules(AIM)and natural bond orbital(NBO)analyses were also employed to qualitatively characterize the single electron bond interactions.The stabilization energy was partitioned via the localized molecular orbital energy decomposition analysis(LMOEDA)method,and both electrostatic and exchange interactions were seen to be major driving forces for the complex stabilization.Interestingly,the sum of the energy contributors of exchange(EEX),repulsion(EREP),polarization(EPOL),dispersion(EDIS)is close to zero and the changes in the interaction energy follow the trend of the electrostatic energy(EES).We observe several linear relationships among the optimized intermolecular parameters and the interaction energies of the various complexes.     

直接键连C-X(X=H, C)的核自旋偶合常数的理论研究

利用建立的PM3级别上的最大重迭对称性分子轨道法和自然杂化轨道方法，计算了系列烃类化合物的杂化轨道和电荷分布，拟合出计算C-H及C-C偶合常数的简单关系式，研究了各种烃类分子中不同的C-Ｈ键和Ｃ-Ｃ键偶合常数，理论计算值和实验数据都较为吻合. 进一步验证了直接键连1JCX(X=C, H)偶合常数主要取决于偶合作用中的Fermi接触相，为从简单价键理论角度解释和计算1JCH和1JCC提供了一种简便直观的方法. 计算结果也表明提出的计算方法是可行的.     

自由基介导C—H键环化合成吲哚酮的研究进展

吲哚酮及其衍生物广泛分布在自然界中,其合成方法研究是当前合成化学领域中的热点之一.按照偶联的方式及其相关的机理,对近几年来自由基介导C—H键环化合成吲哚酮研究进行了归纳,从催化剂、氧化剂和溶剂等反应条件对反应体系的影响出发,讨论了C—H键的切断方法.