纳米尺寸团簇Ni_nZr_n(n=3～5)的几何结构与成键规律研究

根据化学键理论与拓朴原理 ,设计了团簇 Nin Zrn(n=3～ 5 )的可能几何构型 ,并用从头算方法进行构型优化 .结果表明 :由 Ni Zr组成的团簇原子间的 Zr—Zr和 Zr— Ni键明显较强 ,而 Ni—Ni的成键较弱 ;并发现 Nin Zrn(n=3～ 5 )团簇电子性质与有机烯烃分子等瓣相似 ,原子之间的成键按照强弱相间的规则分

一种浮动复合型人工鱼巢

一种浮动复合型人工鱼巢，包括浮动框架，在浮动框架的四周设有多个固定装置，并且浮动框架与固定装置之间是采用活动连接，在浮动框架上分布设有多根缆绳，在缆绳的端部固接有沉子，在沉子与浮动框架之间的缆绳上固定连接多个粘附基质，本实用新型提供一种能为产粘性卵鱼类提供产卵场所的浮动复合型人工鱼巢，能有效促进鱼类资源的保护和可持续利用。</p

Ab Initio Study on Photolysis of Chlorine Nitrate and Its Isomers(Ⅱ) ——Investigation of Reaction Mechanism of ClONO 2ClO+NO 2

用从头算方法讨论了大气臭氧层主要破坏物ClOnO2在光照下分解反应途径：ClOnO2→ClO＋nO2的反应机理.该反应的2个过渡态ClO…nOO（TS2A）和OCl…nOO（TS2b）中TS2A能垒较高，始态难于越过如此高的势垒；TS2b势垒较低，而产物到过渡态TS2b的能垒也仅有1.20EV，故预测该反应为一个可逆反应.The reaction mechanism of photolysis For chlorine nitrate that causes ozone lost in the stratosphere ClONO 2ClO+NO 2 has been studied by using ab initio calculation method.Two transition states TS2a and TS2b have been Found, but it is diFFicult to overcome so high energy barrier to get to TS2a, and it is easy to pass TS2b over 4.20￣4.35 eV energy barrier From the initial state(conFormation (B) or (D)) to the Final state.However only 1.20 eV is required to pass TS2b From ClO+NO 2 to ClONO 2, so reaction path (2) is a reversible reaction.国家自然科学基

Isospectral Molecule

[中文文摘]本文根据HG的约化、变形和交替烃的图形方法,建立了一种研究分子同谱性质的有效图解法。应用图解法可以直观、简便地判断同谱分子,并能直接找出一个HG的同谱点和无约束点,构造出共轭分子的同谱图。这种图形方法又使Herndon等人提出的判断同谱点和无约束点方法得到群理论根据。[英文文摘]Based upon the reduction and transformation of Huckel graph and the graphical method of AH, an effetive diagrammatic method for the study of the cospectral properties of conjugated molecules is established in this paper. The application of this graphical method gives a judgment for the study of isospectral molecules in a simple and direct manner, and provides a direct method for the determination of isospectral points and unrestricted points on Huckel graph, and consequently, provides a method for construct the isospectral graphy of the conjugated molecules.Moreover,this graphical method provides a group theoretical interpretation of Herndon's criteria for the isospectral points and unrestrieted points

Molecular Orbital heoretical Study on Activation of Molecular Nitrogen by Binuclear Zirconium Complex

平面型的侧基配位双核锆分子氮络合物｛［1-PrPCH＿2SIME＿2）＿2n］zrCl｝＿2（μ-￣2η：η￣2-n＿2）的电子结构、成键图象以及锆碎片络合物与分子氮轨道相互作用是通过量子化学SCC-dV-XA计算得到的，结果表明这类前过渡金属原子的d轨道和分子氮1π＿g轨道之间有较强的d-π作用，以致对分子氮有显著的活化作用.The quantum chemical SCC-DV-Xα calculation is perFormed on the pla-nar side-on-bonded coordination binuclear zirconium complex with nitrogen{[[i-Pr_2PCH_2SiMl_2)_2N] ZrCl}_2(μ-η￣2:η￣2-N_2).The electronic structure,bonding pattern and detailsof various orbital interactions between metal zirconium and molecular nitrogen have been ob-tained.The result shows strong d-π orbital interaction between d orbital on metal zirconiumand 1π_g orbital of molecular nitrogen,which results in remarkable activation of nitrogen.国家自然科学基

Graphical Methods of the MO Theory of AH

[中文文摘]本文把交替烃分子轨道成对定理推广到类二色图的约化HG,从而统一了二元均杂共轭体系与其等共轭体系的分子轨道计算,并利用有星标图形和无星标图形,提出交替烃分子轨道图解法,进一步简化了交替烃的HMO计算。[英文文摘]In this article we extend the pairing theorem of the MO theory of AH to the bicolorable reduced Huckel graph, and also unify the MO calculations of the conjugated system composed of alternating groups and that of its corresponding isoconjugate system. In addition, fay the usse of starred and unstarrcd graph, a graphical method of the MO method of AH is proposed, and HMO calculations of AH can be further simplified

Graphical Method of π-Electron Energy Spectrum with Conjugation in Straight Chain Molecule oS Polymer

[中文文摘]对于直链共轭高聚物分子π电子能谱的HMO计算,本文根据一个近似的计算模型,即把这类分子看作具有C_∝轴对称性的共轭体系,使之可利用C_K铀对称性约化共轭体系的Huckel图形(HG),从而迅速、直观地计算一些典型直链共轭高聚物分子的π电子能谱。[英文文摘]Based Upon an approximate mode for the HMO calculations of π-electron energy spectrum with conjugation in straight, chain molecule of polymer, these conjugated molecules may be considered as a conjugated system with C∞ rotation symmetry, and then, by the use of the C∞ rotation symmetry for the reduction of the HuCkel graph, the π-electron energy spectrum of the conjugated polymer can be calculated readily and directly

Ab initio study on photolysis of chlorine nitrate and its isomers (II) - Investigation of reaction mechanism of ClONO2 -> ClO+NO2

The reaction mechanism of photolysis for chlorine nitrate that causes ozone lost in the stratosphere ClONO2 --> ClO + NO2 has been studied by using ab initio calculation method. Two transition states TS2a and TS2b have been found, but it is difficult to overcome so high energy barrier to get to TS2a, and it is easy to pass TS2b over 4.20 similar to 4.35 eV energy barrier from the initial state(conformation (B) or (D)) to the final state. However only 1.20 eV is required to pass TS2b from ClO+NO2 to ClONO2, so reaction path (2) is a reversible reaction

The Properties of Chemical Bonds of the Cluster-compounds with μ_3-S and Quasi-plane-quarternary-nuclear-cobalt

具有64个价电子的含μ_3-S的平面型四核钴簇合物是偏离通常的电子计数规则。为探索其簇骼化学键特性，我们采用量子化学的CndO/2-lMO方法计算其电子结构。结果表明，μ_3-S分别与三个钴原子形成三个双中心键，近似平面型的四个钴原子的P轨道形成两个P-π共轭分子轨道，64个价电子均处于成键轨道上。The cluster-compounds,including 64 valence electrons,with μ_3-S and quasi-plane-quarternary-nuclear-Co do not Follow the general rule of electron count.To investigate the properties of chemical bonds of the cluster-Frame,their electronic structures were calculated with quantum chemical method, CADO/2-LMO.The results indicated that the μ_3-S Formed three double-center bonds with three cobalt atoms,respectively.The p orbits of Four cobalt atoms with approximate plane type Formed two p-π conjugate molecular orbits in which all 64 valence electrons distributed on the binding molecular orbits.国家自然科学基金;结构化学国家重点实验室资

Quantum Chemistry Study on the Formation of Clusters Ni_xZr_(n-x) (n≤6) in Metallic Glass

根据化学键理论与拓朴原理 ,设计了 Nix Zr6 -x团簇的可能几何结构 ,并用从头算方法进行了构型优化 .结果表明 ,小团簇 Nix Zrn-x(n≤ 5)倾向于生成平面结构 ,而 6原子团簇则是八面体或三棱柱构型更稳定 .在大部分情况下 Zr原子把电荷转移给 Ni原子Fourteen Ni xZr 4-x , sixteen Ni xZr 5-x and twentythree Ni xZr 6-x clusters were proposed with chemical bond theory and topological principle and then optimized geometrically with ab initio calculations. It has been shown that nickel atoms tend to combine with zirconium atoms to form plane structure in small clusters(n≤5), but the six atom cluster enjoys to take shape of octahedron or triprism. In many cases the charge transfer is from zirconium atom to nickel atom.国家自然科学基金!(29892166,29983001);; 教育部博士点基金资助项