共查询到20条相似文献,搜索用时 671 毫秒
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P10原子簇的电子结构 总被引:4,自引:0,他引:4
利用Gaussian-94从头算程序,选择6-31G ̄*基组对P_10原子簇的3种构型P_10(C_2v)、P_10(D_5h)与P10(C_3v)进行几何全优化。3种构型总能量相对值表明,原子簇P10(C_3v)具有热力学稳定性;HOMO与LUMO的能级差表明,原子簇P_10(C_3v)具有动力学稳定性。相反,原子簇P_10(D_5h)LUMO的能级值较低,易于得到电子而成为负离子。 相似文献
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用量子化学计算方法MNDO和AM1研究了具有Oh对称性的碳笼烯C32和碳笼烷C32H32的几何结构和电子结构及其稳定性,AM1水平下,评论C32的基态性质和分子振动。 相似文献
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P6(D6h)和P12(D6h的从头算研究 总被引:2,自引:1,他引:2
利用Gaussian-92从头算程序,在6-31G ̄*基组下优化P_6(D_6h)分子和P_(12)(D_(6h))原子簇,并进行了振动频率的计算.得到2P_6(D_(6h))→P_(12)(D_(6h))总能量的相对值,即△E=E_P_(12_(D_(6h))-2EP_6(D_(6h))=-1.197eV. P_(12)(D_(6h))原子簇较2P_6(D_(6h))分子在热力学上更为稳定。基组下,Hp=HP优化的P=P双键键长为0.2005nm,H2P─PH2优化的P─P单键键长为0.2214nm,显然,P6(D6h)分子中的键长比优化双键长0.0091nm,比优化单键短0.0118nm,对于P6(D6h)分子而言,其键长介于单、双键之间且相等。P6分子前线轨道的第39条分子轨道形式估算为:联系人及第一作者:冯健男,男,25岁,博士研究生。 相似文献
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本文用从头计算方法研究了含32个顶点的硼烷B32H32^0^.^2^-及裸原子簇B32与C2B30的构型,稳定性及反应活性,B32的优化计算结果表明,12个5配位与20个6配位两类硼原子不在同一球面时最稳定,而且所含两种B-B核间距离(R56,R66)的优化值验证了Lipscomb的经验数值,B32,B3232^2^-电子结构及原子布居的计算表明骨架成键轨道满足Wade规则。相应的计算还表明,中性 相似文献
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Cun,Agn,Aun(n=2,3,4)原子簇结构的理论分析 总被引:1,自引:0,他引:1
在应用DV-Xa自洽场方法研究Cun,Agn,Aun原子簇电子结构基础上,分析了原子簇中原子轨道间的相互作用及其大小随几何构型的变化,并讨论了原子簇的Xa总能量与原子簇几何构型的关系,采用单、双过渡态理论方法分别计算原子簇分子轨道的电离能和分子轨道的电子跃迁能,结果表明Agn的电离能计算值与实验值符合较好,而Aun原子簇则有一定偏差,这可能是由Aun的较大相论效应引起的,Ag4的电子跃迁能与实验值 相似文献
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本文用从头计算方法研究了含32个顶点的硼烷及裸原子簇B32与C2B30的构型、稳定性及反应活性。B32的优化计算结果表明,12个5配位与20个6配位两类硼原子不在同一球面时最稳定,而且所含两种B-B核间距离(R_(56)R_(66))的优化值验证了Lipscomb的经验数值。B32、B_(32)H_(32)~(2-)电子结构及原子布居的计算表明骨架成键轨道满足Wade规则.相应的计算还表明,中性B_(32)H_(32)可能稳定存在,但构型的对称性将低于Ik对称,另外.对C2B30结合能的计算及前线轨道性质的分析表明,C2B30热稳定性较高,并且有较强的得电子反应活性。 相似文献
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原子连接次序的一些经验规则 总被引:1,自引:0,他引:1
在有关物质分子结构的教学中 ,经常有学生问起一些类似这样的问题 :(1)次磷酸H3PO3与PF3是等电子体 ,H3PO3为什么具有 POHO OHH的四面体结构而不与PF3相似呈 P··HO OHOH的三角锥结构(2种结构式中的P都为 + 3氧化态 ,都是sp3杂化 ) ;(2 )N2 O为什么具有线性的··N—N—O· · ··· ·· ···结构 (方框表示π4 3键 ) ,但具有同样线性和键级的结构··N—O—N· ·· ·· ·· ···却不存在 (2种结构式中中心原子的N、O均为sp杂化 ) ;(3)CO与HCN也相当于等电子体 ,CO的结构… 相似文献
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The convergence of parallel tempering Monte Carlo simulations of the 38-atom Lennard-Jones cluster starting from the Oh global minimum and from the C(5v) second-lowest-energy minimum is investigated. It is found that achieving convergence is appreciably more difficult, particularly at temperatures in the vicinity of the Oh --> C(5v) transformation when starting from the C(5v) structure. A strategy combining the Tsallis generalized ensemble and the parallel tempering algorithm is implemented and used to improve the convergence of the simulations in the vicinity of the Oh --> C(5v) transformation. 相似文献
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Wei M He C Hua W Duan C Li S Meng Q 《Journal of the American Chemical Society》2006,128(41):13318-13319
A large protonated water cluster, H+(H2O)27, has been trapped and stabilized within the well-modulated cavity of a 3D metal-organic framework formed by cobalt(II) and 4,4'-bipyridine-N,N'-dioxide with a globular Keggin structure [PW12O4]3- anion as template. The structurally characterized protonated water cluster might comprise a (H2O)26 shell with Oh symmetry and a monowater core within the center which is suggested to be a hydronium ion with the Eigen model. 相似文献
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为探究团簇Ni4P催化析氢最强的结构,基于密度泛函理论,在B3LYP/Lan12dz水平下,对团簇Ni4P的初始构型进行计算和优化,得到5种优化构型。从热力学稳定性、前线轨道图和前线轨道能级差对团簇Ni4P的析氢性能分析发现,构型1(4)和1(2)的热力学稳定性较强;团簇Ni4P各优化构型均易吸附水中的氢原子,Ni原子为团簇Ni4P催化活性位点,且构型1(4)、1(2)和2(4)催化析氢的活性更强。(1(2))-H、(2(2))-H在电化学脱附法和化学重组法中均具有较强的催化活性。以上说明构型1(2)是团簇Ni4P催化析氢最强的结构。 相似文献
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Large single crystals of oxygen-deficient Sr6Co5O(15-delta) compounds, i.e., Sr6Co5O14.70 and Sr6Co4.9Ni0.1O14.36, were obtained by using K2CO3 flux in the presence of additives of transition metal oxides. The single-crystal structure determination shows that the structures of Sr6Co5O14.70 and Sr6Co4.9Ni0.1O14.36 crystallize in the space group R and can be described as one-dimensional face-sharing CoO3 polyhedral chains and Sr cation chains. Unlike the other known 2H-perovskite-related oxides in which the polyhedral chains consist of octahedra (Oh) and trigonal prism (TP), the structure of Sr6Co5O14.70 and Sr6Co4.9Ni0.1O14.36 contain Oh and intermediate polyhedra (IP) and can be attributed to a general structure formula A6A'2B3O(15-delta), which is closely related to the known A6A'B4O15 phases by shifting of a B atom and the O3 triangle along the c axis. Further study on O3 reveals that this oxygen position splits into two independent positions, corresponding to polyhedral geometry of IP and TP, respectively. Therefore, the polyhedral chain in the structure should be more precisely described as a random composite of the 4Oh + TP and 3Oh + 2IP. This model is used to interpret the magnetic properties, although not quantitatively. The 4-D structure analysis was also conducted for both Sr6Co5O14.70 and Sr6Co4.9Ni0.1O14.36 with a commensurate modulated structure in a 4-D superspace group, R3m(00gamma)0s, gamma = p/k = 3/5. By considering the same 4-D superspace group R3m(00gamma)0s but different t-phases, one can understand the structure relationship between Sr6Co5O14.70 and Sr6Rh5O15. 相似文献
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Shang‐Fu Yuan Cong‐Qiao Xu Jun Li Quan‐Ming Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(18):5967-5970
A golden fullerene Au32 cluster has been synthesized with amido and phosphine ligands as the protecting agents. Single‐crystal X‐ray structural analysis revealed that this gold nanocluster, [Au32(Ph3P)8(dpa)6] (SbF6)2 (Hdpa=2,2′‐dipyridylamine), has a stable pseudo‐Ih Au328+ core with S6 symmetry, which features an Au12@Au20 Keplerate cage co‐protected by Ph3P and dpa ligands. Quantum‐chemical studies were conducted to elucidate the origin of the special stability of this cluster, and suggest that it is electronically stabilized through metal–ligand interactions. 相似文献
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According to the structure features of Fe80P20, A series of clusters Fe4P were designed and focused on studying the stability of local structure, charge distribution and chemical bond. Using the DFT method,energy and structure of Fe4P clusters were optimized and analyzed. The computational results showed that the energy of cluster 1(2) has the lowest energy, and the possibility of its existence in the Fe8oP20 is high. Analyzing the transition states among the clusters, it was found that the clusters in the doublet state are more stable than those in the quartet state. The numbers of the Fe-P bond in the clusters play important roles in the cluster stability and electrons transfer properties. The more numbers of Fe-P bonds in the clusters, the higher the cluster stability, and the weaker the ability of P atom to get electron. The number of Fe atoms, which has bonding interactions with the P atom, is direct proportional to the average 3d orbit population of Fe atom. Basing on the orbital population, average magnetic moments of each Fe atom in the Fe4P clusters were calculated, and they are all smaller than that of single metal Fe atom. This suggests that all Fe4P clusters have soft magnetic property and they are expected to be perfect material for preparing soft magnetic apparatus. 相似文献
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Li WQ Tian WQ Feng JK Liu ZZ Ren AM Zhang G 《The journal of physical chemistry. A》2005,109(37):8391-8397
Cationic cluster Ti2P6+ has been studied within density functional theory. The structure of this cluster is predicted to be a slightly distorted tetragonal prism. The dissociation energy of this cationic cluster is higher than that of the known sandwich compound, [(P5)2Ti]2-, because of the different bonding in these two compounds. In Ti2P6+, the hybridization of P atoms of the ring is sp3. The bonding between the metal atoms and the P ring is mainly sigma-pi. While in [(P5)2Ti]2-, the P atoms take sp2 hybridization, the bonding between the metal atom and the rings is the typical pi-pi interaction. The electronic delocalization is another stabilizing factor for Ti2P6+. The nuclear independent chemical shift indicates that Ti2P6+ is a three-dimensional aromatic molecule. The predicted infrared and NMR help to identify the Ti2P6+ conformations in experiment. 相似文献