氧原子在银原子簇表面吸附重构的DFT研究

选取三层原子簇模型模拟Ag(110)表面,采用量子化学的电子密度泛函方法(DFT)研究了氧原子吸附在Ag(110)表面而引起银表面的多种重构现象。通过计算体系结合能优化得到吸附后体系的表面几何构型,并给出了相关的电离能、电子跃迁能。计算表明：氧原子吸附在银原子的长桥位上,位于银表面之上约0.4　处,氧原子的吸附引起银原子表面强烈弛豫。第一、二层银原子间距扩张;第二、三层银原子间距收缩。由于氧原子的吸附,第一层银原子出现丢失行现象,第二层银原子出现两两成对现象,而第三层银原子出现弯曲现象。     

卤化氢HX（X=F,Cl,Br,I）与C2H2相互作用本质的量子化学研究

在MP2水平上,采用全电子基组,对C2H2与HX(X=F,Cl,Br,I)相互作用进行了研究.构型优化同时进行频率验证,得到4个T型结构的稳定复合物,相互作用能在-12.761～-7.086kJ/mol之间.自然键轨道(NBO)与分子中的原子(AIM)理论分析表明,形成复合物分子间的电荷转移量都很少,最大仅为0.009a.u.,作用强度与氢键类似.对称性匹配微拢理论(SAPT)能量分解数据表明,对于C2H2…HX(X=F,Cl,Br,I)体系,从F到I,静电作用逐渐减弱,色散作用逐渐增强;相互作用能中对吸引能的贡献主要为静电能和色散能,二者之和占到80%以上,诱导能所占的比例很小,卤化氢与乙炔分子间相互作用的本质为静电作用和色散作用.     

B…HY/BrY(B=C4H4,C6H6,Y=F,Cl,Br)分子间作用的电子密度拓扑研究

运用MP2/aug-cc-pVDZ对B…HY氢键复合物和B…BrY卤键复合物(B=C4H14,CdH6,Y=F,Cl,Br)的几何构型及相互作用能进行了研究.研究发现对于相同的路易斯碱来说,B…HY和B…BrY的几何构型非常类似,B…BrY卤键键能大于B…HY氢键键能.电子密度拓扑分析表明C4H4(S)…BrY,C4H4(T).…BrF之间的卤键作用介于离子键和共价键之间,其余的氢键和卤键作用均为闭壳层相互作用.形成氢键和卤键后,卤化氢和双卤分子的原子积分性质都发生了变化,B…HY中H原子能量增加,而B…BrY中Br原子能量减少.     

可见光驱动的偶氮苯分子开关的理论设计与计算模拟

可见光驱动的偶氮苯等光致异构材料在生物探针和传感体系、光敏电池以及储能材料等领域有重要的应用前景.采用密度泛函理论(DFT)以及反应性分子动力学方法,研究了卤素原子(F,Cl,Br,I)四邻位取代的4,4′-乙酰胺偶氮苯衍生物分子的几何结构与光学性能之间的关系.DFT计算表明,卤素原子F,Cl,Br,I的邻位四取代不同程度地使其反式异构体的偶氮苯分子平面发生扭曲,导致在可见光范围内均出现了明显的吸收峰.另外,应用反应性分子动力学模拟了卤素(F,Cl,Br,I)-4,4′-乙酰胺偶氮苯分子的顺反可逆异构过程,其反式到顺式的构型转换率在46%~86%之间,与实验现象定性相符.     

EHMO研究乙烯氧化反应的银-金合金催化剂

文献上关于乙烯被银催化氧化的机理研究结果表明,乙烯与被吸附的分子氧作用生成环氧乙烷,而与解离的原子氧作用生成二氧化碳和水. 在一种纯金属中加入其它金属形成合金时,将改变原金属的电子结构和几何构型。而对金属催化剂来说,其电子结构和几何构型的变化,将影响其吸附和吸附时形成的     

Cun,Agn,Aun（n=2,3,4）原子簇结构的理论分析

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     

超碱金属复合物Al7X0/-（X=F,Cl,Br,I）的结构及非线性光学性质的理论研究

采用密度泛函理论(DFT)方法研究了一系列超碱金属复合物Al7X0/-(X=F,Cl,Br,I)的几何结构及二阶非线性光学(NLO)性质.结果表明,不同卤素的连接对Al0/-7簇的几何构型影响均很小.计算得到Al7X和Al7X-体系的垂直电离能(VIE)均低于Cs原子的第一电离势(IP=3.90 eV),表明这些体系具有超碱金属的性质,可称其为超碱金属.此外,采用CAM-B3LYP,M06-2X和PBE0等3种泛函计算了该体系的非线性光学性质,结果显示,上述体系均具有较大的第一超极化率(β0),其中Al7I-的β0值为21679 a.u.,是已知超碱金属复合物BLi6F(11459 a.u.)的1.9倍.值得注意的是,该类体系的第一超极化率随着卤素电负性的减小而增大,即Al7F0/-相似文献   

载铜活性炭吸附一氧化碳的密度泛函理论计算

应用密度泛函理论和相对论有效核势方法, 用C₁₆H₁₀, C₁₃H₉, C₁₂H₁₂原子簇模型模拟活性炭表面, 计算得到了CO在载铜活性炭上的吸附位、吸附构型和吸附能. 研究表明: 载铜活性炭吸附CO的过程, 本质上是Cu(I)通过σ-π配键与CO络合, 形成Cu—C键的过程. 载铜活性炭对CO的络合吸附能在50～60 kJ/mol之间, 远大于活性炭对CO的物理吸附能(9.15 kJ/mol), 因而络合吸附更稳定, 选择性也更高. Cu(I)选择吸附在活性炭表面的顶位和桥位, 一个Cu(I)至多可以吸附一个到两个CO分子, 但吸附一个CO比吸附两个CO稳定.     

苯在Si(111)-7*7表面化学吸附的理论研究

采用两种大小不同的原子簇模型Si_(30)H_(28)和Si_(13)H_(16),分别用两层 ONIOM方法（对较大原子簇）和普通量子化学方法（对较小原子族）考察了苯分子 在Si(111)-7 * 7表面的化学吸附。对三种可能的吸附物种分别用DFT或HF方法进行 了计算。通过大小原子簇吸附物种的吸附能以及几何构型优化参数的比较发现,对 于稳定的吸附物种,较小的原子簇基本上可以代替较大的原子簇进行计算,而对于 不太稳定的吸附物种,就不得不考虑周边原子的影响。计算结果表明苯在Si(111)- 7 * 7表面的主要吸附种是双σ成键的1,4加成产物,不稳定的单吸附物种可能是 1,4加成物种的前驱态。     

铜族金属与完整及氮掺杂石墨烯的相互作用

基于广义梯度密度泛函理论和周期平板模型,研究了铜族金属单原子和双原子簇与完整及氮掺杂石墨烯的结合情况.结果表明,氮掺杂后石墨烯的电子结构特性由半金属性变为金属性;铜族金属在完整及石墨型氮掺杂石墨烯上的吸附较弱,结合能约为0.5eV,而在吡啶型氮掺杂和吡咯型氮掺杂石墨烯上有较强的化学吸附,结合能一般大于1eV;吡咯型氮掺杂后的构型不稳定,金属原子及簇与包含该结构的石墨烯衬底作用时会使其向吡啶型氮掺杂转变,并最终得到基于吡啶型氮掺杂的稳定吸附构型.Mulliken电荷布居分析显示,吸附在吡啶型氮掺杂石墨烯上的金属单原子与金属双原子簇带电性质相反.态密度及轨道分析表明,Cu与吡啶型氮掺杂石墨烯空位处留有悬挂键的三个原子成键,而Au与其中两个C原子成键.     

Ionization energies of K2X (X = F,Cl, Br,I) clusters

The electronic structure and properties of dipotassiummonohalides are important for understanding the unique physical and chemical behavior of M_nX systems. In the present study, K₂X (here X = F, Cl, Br, I) clusters were generated in the vapor over salts of the corresponding potassium halide, using a magnetic sector thermal ionization mass spectrometer. The ionization energies obtained for K₂F, K₂Cl, K₂Br, and K₂I molecules were 3.82 ± 0.1 eV, 3.68 ± 0.1 eV, 3.95 ± 0.1 eV, and 3.92 ± 0.1, respectively. These experimental values of ionization energies for K₂X (X = F, Br, and I) are presented for the first time. The ionization energy of K₂Cl determined by thermal ionization corresponds to previous results obtained by photoionization mass spectrometry, and it agrees with the theoretical ionization energy calculated by the ab initio method. The presently obtained results support previous theoretical predictions that the excess electron in dipotassiummonohalide clusters is delocalized over two potassium atoms, which is characteristic for F‐center clusters. Copyright © 2011 John Wiley & Sons, Ltd.     

A density functional theory study on the Ag<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>H (<Emphasis Type="Italic">n</Emphasis> = 1–10) clusters

Density functional GGA-PW91 method with DNP basis set is applied to optimize the geometries of Ag _n H (n = 1–10) clusters. For the lowest energy geometries of Ag _n H (n = 1–10) clusters, the hydrogen atom prefers to occupy the two-fold coordination bridge site except the occupation of single-fold coordination site in AgH cluster. After adsorption of hydrogen atom, most Ag _n structures are slightly perturbed and only the Ag₆ structure in Ag₆H cluster is distorted obviously. The Ag–Ag bond is strengthened and the strength of Ag–H bond exhibits a clear odd–even oscillation like the strength of Au–H bond in Au _n H clusters, indicating that the hydrogen atom is more favorable to be adsorbed by odd-numbered pure silver clusters. The adsorption strength of small silver cluster toward H atom is obviously weaker than that of small gold cluster toward H atom due to the strong scalar relativistic effect in small gold cluster. The pronounced odd–even alternation of the magnetic moments is observed in Ag _n H systems, indicating that the Ag _n H clusters possess tunable magnetic properties by adsorbing hydrogen atom onto odd-numbered or even-numbered small silver cluster.     

Structural and Electronic Properties in Titanium-Doped Stannum Clusters: Comparison with Their Anions and Cations

The neutral, anionic, and cationic Sn_nTi^{(0, ±1)} (n?=?1–10) units are researched computationally using a density functional theory. The optimized geometries of Sn_nTi^{(0, ±1)} clusters illustrate that the most stable structures between the neutral, anionic, and cationic clusters keep the similar structures when n?=?1, 2, 4, 5, 9,10, however, we find that the obtained most stable clusters of the size n?=?3, 6, 7, 8 are different. From the optimized results a systematic analysis is carried out to obtain the relative stabilities, electronic properties, and natural population analysis of Sn_nTi^{(0, ±1)} clusters. The relative stabilities are investigated by analyzing the binding energies, fragmentation energies, and the second order energies difference of Sn_nTi^{(0, ±1)} clusters, the results show that the binding energies of anionic clusters are obviously larger than those of neutral and cationic clusters. The HOMO–LUMO gap, the adiabatic electron affinity, vertical electron detachment energy, adiabatic ionization potential energy, and vertical ionization potential energy respond the electronic property, we obtain that the Ti atom changes the electron structures of stannum clusters. To discuss reliable charge transfer information from Sn_nTi clusters to Sn_nTi^? clusters and Sn_nTi⁺ clusters, the natural population analysis of neutral, anionic, and cationic Sn_nTi^(0,±1) clusters are calculated.     

Dependence of Property of Silver Nanoparticles within Dendrimer-template on Molar Ratios of Ag+ to PAMAM Dendrimers

G5.0‐OH PAMAM dendrimers were used to prepare fluorescent silver clusters with weaker ultraviolet irradiation reduction method, in which the molar ratio of Ag⁺ to PAMAM dendrimers was the key factor to determine the geometry and properties of silver nanoparticles. The results showed that because of G5.0‐OH PAMAM dendrimers as strong encapsulatores, when the molar ratios of Ag⁺ to PAMAM dendrimers was smaller than 5, the obtained Ag_n clusters (n<5) had line structures and "molecular‐like" properties, which were highly fluorescent and quite stable in aqueous solution. Whereas when the molar ratios were between 5 and 8, the obtained Ag_n clusters were 2D structures and their fluorescence was weaker. When the molar ratio was larger than 8, the structure of silver nanoparticles was 3D and no fluorescence was observed from the obtained silver nanoparticles.     

The Geometric Structure of Silver‐Doped Silicon Clusters

Cationic silver‐doped silicon clusters, Si_nAg⁺ (n=6–15), are studied using infrared multiple photon dissociation in combination with density functional theory computations. Candidate structures are identified using a basin‐hopping global optimizations method. Based on the comparison of experimental and calculated IR spectra for the identified low‐energy isomers, structures are assigned. It is found that all investigated clusters have exohedral structures, that is, the Ag atom is located at the surface. This is a surprising result because many transition‐metal dopant atoms have been shown to induce the formation of endohedral silicon clusters. The silicon framework of Si_nAg⁺ (n=7–9) has a pentagonal bipyramidal building block, whereas the larger Si_nAg⁺ (n=10–12, 14, 15) clusters have trigonal prism‐based structures. On comparing the structures of Si_nAg⁺ with those of Si_nCu⁺ (for n=6–11) it is found that both Cu and Ag adsorb on a surface site of bare Si_n⁺ clusters. However, the Ag dopant atom takes a lower coordinated site and is more weakly bound to the Si_n⁺ framework than the Cu dopant atom.     

含亚胺和胆甾烯基不对称液晶二聚体的合成及介晶性

报道含亚胺和胆甾烯基不对称液晶二聚体化合物XC₆H₄N＝CHC₆H₄OC₁₀H₂₀COOCh* [X＝OC_nH_2n＋1, (n＝1～12,14), F, Cl, Br, CH₃] (1a～1q)的合成及液晶性. 目标化合物通过600 MHz ¹H NMR和元素分析进行了结构表征. 其介晶性通过偏光显微镜(POM)和差示扫描量热计(DSC)进行了研究. 结果显示: 所有化合物都具有胆甾相(N*). 对于烷氧基系列(X＝OC_nH_2n＋1), 有部分化合物还呈现了近晶A相(S_A), 且随着末端烷氧链长度的增加, 化合物的清亮点呈现缓慢下降的趋势, 而化合物从胆甾相到各向同性液体转变的熵变(ΔS_N*→I)则呈现奇-偶效应. 同时我们对比研究了取代基X对胆甾相稳定性的影响, 发现取代基X对胆甾相的稳定性高低顺序为: MeO＞Cl＞Br＞Me＞F. 这些结果证实了末端取代基的改变对化合物的相转变温度以及介晶性质有显著的影响.     

Density functional study of AgnPd and AgnPdH clusters

Small Ag_nPd (n = 5) clusters and their hydrides Ag_nPdH (n = 5) have been studied by density functional theory calculations. For bare clusters, the structures in which the Pd atom has a maximum number of neighboring Ag atoms tend to be energetically favorable. Hydrogen prefers binding to Ag? Pd bridge site of Ag_nPd clusters except for Ag₅Pd. The binding energy has a strong odd–even oscillation. The electron transfers are from Ag atoms to Pd in bare clusters and are from metal clusters to H in cluster hydrides. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Synthesis of Silver Complexes in DMSO–HX and DMSO–HX–Ketone Systems

Comparative analysis of the oxidizing and complexing properties of the DMSO–HX (X = Cl, Br, I) and DMSO–HX–ketone (X = Br, I; the ketone is acetone, acetylacetone, or acetophenone) systems toward silver was performed. The reaction products are AgX (X = Cl, Br, I), [Me₃S⁺]Ag _n X^– _m (n= 1, 2; m= 2, 3; X = Br, I) and [Me₂S⁺CH₂COR]AgX^– ₂(R = Me, Ph; X = Br, I). The composition of the obtained complexes depends on both the DMSO : HX ratio and the nature of HX, as well as on the methods used to isolate solid products from the solution. It was noted that the formation of the [Me₂S⁺CH₂COMe]AgBr^– ₂complex in the Ag⁰–DMSO–HBr–acetylacetone system occurs with cleavage of the acetylacetone C–C bond and follows a specific reaction course. The optimum conditions for production of the silver compounds in the title systems are determined.     

Stability of AgIII towards Halides in Organosilver(III) Complexes

The involvement of silver in two-electron Ag^I/Ag^III processes is currently emerging. However, the range of stability of the required and uncommon Ag^III species is virtually unknown. Here, the stability of Ag^III towards the whole set of halide ligands in the organosilver(III) complex frame [(CF₃)₃AgX]⁻ (X=F, Cl, Br, I, At) is theoretically analyzed. The results obtained depend on a single factor: the nature of X. Even the softest and least electronegative halides (I and At) are found to form reasonably stable Ag^III−X bonds. Our estimates were confirmed by experiment. The whole series of nonradiative halide complexes [PPh₄][(CF₃)₃AgX] (X=F, Cl, Br, I) has been experimentally prepared and all its constituents have been isolated in pure form. The pseudohalides [PPh₄][(CF₃)₃AgCN] and [PPh₄][(CF₃)₃Ag(N₃)] have also been isolated, the latter being the first silver(III) azido complex. Except for the iodo compound, all the crystal and molecular structures have been established by single-crystal X-ray diffraction methods. The decomposition paths of the [(CF₃)₃AgX]⁻ entities at the unimolecular level have been examined in the gas phase by multistage mass spectrometry (MSⁿ). The experimental detection of the two series of mixed complexes [CF₃AgX]⁻ and [FAgX]⁻ arising from the corresponding parent species [(CF₃)₃AgX]⁻ demonstrate that the Ag−X bond is particularly robust. Our experimental observations are rationalized with the aid of theoretical methods. Smooth variation with the electronegativity of X is also observed in the thermolyses of bulk samples. The thermal stability in the solid state gradually decreases from X=F (145 °C, dec.) to X=I (78 °C, dec.) The experimentally established compatibility of Ag^III with the heaviest halides is of particular relevance to silver-mediated or silver-catalyzed processes.     

Density functional study of structural and electronic properties of maximum‐spin n+1Aun−1Ag clusters

The structures and relative stabilities of high‐spin ⁿ⁺¹Au_n?1Ag and ⁿAu_n?1Ag⁺ (n = 2–8) clusters have been studied with density functional calculation. We predicted the existence of a number of previously unknown isomers. Our results revealed that all structures of high‐spin neutral or cationic Au_n?1Ag clusters can be understood as a substitution of an Au atom by an Ag atom in the high‐spin neutral or cationic Au_n clusters. The properties of mixed gold–silver clusters are strongly sized and structural dependence. The high‐spin bimetallic clusters tend to be holding three‐dimensional geometry rather than planar form represented in their low‐spin situations. Silver atom prefers to occupy those peripheral positions until to n = 8 for high‐spin clusters, which is different from its position occupied by light atom in the low‐spin situations. Our theoretical calculations indicated that in various high‐spin Au_n?1Ag neutral and cationic species, ⁵Au₃Ag, ³AuAg and ⁵Au₄Ag⁺ hold high stability, which can be explained by valence bond theory. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009