Tunneling magnetoresistance of C2H2 molecules sandwiched between Co clusters

The tunneling magnetoresistance (TMR) of samples containing well-defined Co clusters (≈4.5 nm mean diameter) embedded in C₂H₂ matrices essentially is independent of Co-cluster volume fraction v_Co and reveals a value of about 26% at T=2 K. This result is in contrast to that obtained for Co clusters embedded in C₂H₄ matrices (Phys. Rev. B 67 (2003) 094433). In the latter system the TMR strongly decreased with increasing v_Co indicating different possible orientation of the C₂H₄ molecule sandwiched between the Co clusters. We, therefore, conclude that the C₂H₂ molecules are sandwiched in a rather well-defined orientation between the Co clusters. They probably form double layers of C₂H₂ molecules with the C–C bond axis parallel to the Co cluster surface.     

以团簇加连接原子模型解析Cr-C共晶成分

Cr-C体系材料是重要硬质防护涂层的代表,具有共晶特征.我们的前期工作指出,共晶合金满足双团簇近程序结构模型,由两种稳定液体亚单元构成,各自满足理想非晶团簇成分式,这里的第一近邻团簇来自相关共晶相.显然共晶成分解析的关键在于获得团簇,而相结构中往往存在多种团簇,进入到非晶/共晶团簇成分式的主团簇定义是关键环节.本文通过应用Friedel振荡理论及原子密堆,以团簇分布的球周期性及孤立度为判据,以Cr-C共晶相为例,进一步细化了共晶相中的主团簇选择流程,再搭配以2,4或6个连接原子,获得了描述共晶成分Cr_(86)C_(14)和Cr_(67.4)C_(32.6)的双团簇成分式:[Cr-Cr_(14)+C-Cr_9]Cr C_3和[C-Cr_9+C-Cr_8]C_6,其中四种团簇分别来自共晶相Cr,Cr_(23)C_6,Cr_7C_3和Cr_3C_2.该工作进一步证实了团簇加连接原子模型在共晶点解析中的普适性,并从理论上支持了相关的材料设计.     

中性和阳离子丁酮团簇的结构及稳定性的理论研究

使用密度泛函B3LYP方法,在6-31G*和6-311+G**基组水平上计算中性和阳离子丁酮团簇(CH_3COC_2H_5)_n和(CH_3COC_2H_5)_n~+(n 7)的稳定结构,并比较不同尺寸团簇之间的相对稳定性.中性和阳离子丁酮团簇的结构具有相似性:n=3—7时,组成团簇的丁酮的平均几何参数基本相同,单环结构最稳定;随着团簇尺寸的增加,双环结构的稳定性逐渐上升.通过平均结合能、一阶差分能、HOMO-LUMO能隙等计算分析可知:在所研究的各种尺寸团簇中,(CH_3COC_2H_5)_3是最稳定的中性团簇,与实验中的最强峰对应;(CH_3COC_2H_5)_4~+是最稳定的阳离子团簇.通过电离能计算得到丁酮分子的垂直电离能为9.535 eV与实验值相符,同时证明中性和阳离子丁酮二元团簇的结构变化较大.研究结果为实验中丁酮团簇碎片离子的形成机理提供一定的理论依据,并且为进一步研究酮类分子团簇的生长规律提供有价值的信息.     

超声喷流氩氢混合团簇特性研究

利用瑞利散射方法研究了超声喷流Ar-CH4混合团簇和超声喷流Ar-H2混合团簇的特性.通过测量不同混合比例和不同背压下所形成混合团簇的散射信号发现,当用Ar气和CH4的混合气体进行超声喷流时很容易形成Ar-CH4混合团簇,当Ar气含量为50%时混合团簇尺度最大且大于相同气压下纯Ar团簇尺度和纯CH4团簇尺度.实验发现,与纯H2团簇只能在低温条件下获得不同,常温下即可形成Ar-H2混合团簇,实现了常温下含氢团簇的获取,从而有效降低了制备成本.在H2含量大于40%时混合团簇开始形成并在60%时达到最大尺度.含氢(氘)混合团簇在氢(氘)团簇的基础上引入了更重的异核Ar元素,在激光氘团簇聚变实验中它将进一步加速氘离子从而获得更高的能量,并具有更高的中子产额和聚变效率.     

Three-Ni-atom cluster formed by sulfur adsorption on Ni(1 1 1)

Sulfur adsorption on Ni(1 1 1) at room temperature has been studied by scanning tunneling microscopy. Irregularly-shaped islands, which are aggregates of small particles, appear with troughs on (1 1 1) terraces. Estimating the number of small particles in the irregular islands and that of Ni atoms ejected through the formation of troughs, we find that each small particle contains three Ni atoms. A three-Ni-atom cluster is proposed, where three S atoms are adsorbed on 4-fold hollow sites formed on the sides of the cluster. The Ni₃S₃ cluster can assume two orientations on the (1 1 1) surface. We show that the apparently-irregular distribution of small particles is well understood by assuming the alternate orientation of neighboring Ni₃S₃ clusters and the slight energy difference between the two orientations of a single Ni₃S₃ cluster. Real-time observation of a Ni(1 1 1) surface under H₂S ambience reveals that small islands composed of three or four Ni₃S₃ clusters change their positions rapidly, preventing the simple growth of islands at the initially-nucleated positions.     

Ti$lt;sub$gt;2$lt;/sub$gt;B$lt;sub$gt;$lt;i$gt;n$lt;/i$gt;$lt;/sub$gt;($lt;i$gt;n$lt;/i$gt;=1–10)团簇的结构与稳定性:基于从头算的研究

采用密度泛函理论中的B3LYP方法, 结合从头算的CCSD(T)方法对Ti₂B_n(n=1–10)团簇的稳定性和电子性质进行了研究. 发现两个Ti原子的掺杂导致B_n团簇结构发生了根本性变化. 随着n的增大, Ti₂B_n团簇结构生长非常规律. 所有的最稳定结构都可看成双锥结构, 并且两个Ti原子处在双锥结构的锥顶. 根据二阶差分能量分析, 得出Ti₂B_n(n=1–10)团簇的幻数是6, 7和8. 进一步分析了团簇的Ti原子解离能、B原子解离能以及团簇的电子亲和势和电离势. 这些能量分析表明Ti₂B₆团簇既有良好的热力学稳定性, 又有良好的动力学稳定性. 应用前线轨道理论, 对Ti原子与B₆之间的成键进行了分析, 了解其稳定性的根源. 关键词： 2B_n团簇')" href="#">Ti₂B_n团簇 稳定性 从头计算 电子结构     

Polyhedral silver clusters as single molecule ammonia sensor based on charge transfer-induced plasmon enhancement

The unique plasmon resonance characteristics of nanostructures based on metal clusters have always been the focus of various plasmon devices and different applications. In this work, the plasmon resonance phenomena of polyhedral silver clusters under the adsorption of NH₃, N₂, H₂, and CH₄ molecules are studied by using time-dependent density functional theory. Under the adsorption of NH₃, the tunneling current of silver clusters changes significantly due to the charge transfer from NH₃ to silver clusters. However, the effects of N₂, H₂, and CH₄ adsorption on the tunneling current of silver clusters are negligible. Our results indicate that these silver clusters exhibit excellent selectivities and sensitivities for NH₃ detection. These findings confirm that the silver cluster is a promising NH₃ sensor and provide a new method for designing high-performance sensors in the future.     

WnNim(n+m=8)团簇轨道能级与芳香性的理论研究

用密度泛函理论(DFT)中的b3lyp方法,在Lanl2dz基组水平上对W_nNi_m(n+m=8)团簇的各种可能构型进行几何参数全优化,得到它们的基态构型;并对基态构型的轨道能级分布、能隙、HOMO、LUMO能级、芳香性和热力学性质进行分析,结果表明:团簇W₅Ni₃和W₆Ni₂的Alpha轨道和Beta轨道是完全简并的,所有电子都是严格两两配对的;团簇W₂Ni₆能隙最小,化学活性最强,组成前线轨道的成分基本相同;W₆Ni₂能隙最大,化学活性最弱;团簇W₁Ni₇,W₅Ni₃,W₆Ni₂,W₇Ni₁具有芳香性,W₂Ni₆具有反芳香性;团簇的生成焓都是负值,为放热反应,热力学上是稳定的.     

Kinetic Simulation of Fractal Aggregation on Liquid Surfaces

A modified fractal growth model based on the deposition, diffusion, and aggregation (DDA) with cluster rotation is presented to simulate two-dimensional fractal aggregation on liquid surfaces. The mobility (including diffusion and rotation) of clusters is related to its mass, which is given by D_m=D₀ s^-γ_D and θ_m=θ₀s^-γ_θ, respectively. We concentrate on revealing the details of the influence of deposition flux F, cluster diffusion factor γ_D and cluster rotation factor γ_θ on the dynamics of fractal aggregation on liquid surfaces. It is shown that the morphologies of clusters and values of cluster density and fractal dimension depend dramatically on the deposition flux and migration factors of clusters.     

GEOMETRIC AND ELECTRONIC STRUCTURES OF Ti8C12 CLUSTER

The electronic structure of Ti₈C₁₂ clusters with three possible geometric structures suggested in the literature is studied using the discrete-variational local-density-functional method. The results show that the ground states of the clusters are all degenerate, which means further Jahn-Teller distortions for the geometric structures of clusters. The results also indicate that the distorted dodecahedral Ti₈C₁₂ cluster, which is proposed by Guo et al. and optimized by the first principle calculations, is the most stable one among the clusters we considered and its electronic structure can explain the experimental observations. In this cluster, there is a strong pd bonding between Ti and C atoms, and the density of states at the Fermi energy is high.     

(K3N)n(n=1,…,5)团簇结构与性质的密度泛函理论研究

利用密度泛函理论B3LYP方法,在6-311G*水平上对碱金属氮化物(K₃N)_n(n=1,…,5)团簇各种可能构型进行几何结构优化,预测各团簇的最稳定结构,并对其成键特性、电荷分布、振动特性及稳定性进行分析研究.结果表明,随着n的增大,(K₃N)_n(n=1,…,5)团簇的最稳定结构逐渐由平面结构向空间立体结构转变,(K₃N)₄、(K₃N)₅团簇为类似晶体的层状结构;团簇中N原子的配位数以5、6较多见;团簇中N原子的平均自然电荷为-1.608e,K原子的平均自然电荷为+0.550e,K-N键为较强的离子键;(K₃N)₄团簇有相对较高的动力学稳定性.     

First Principle Calculation on AunAg2 （n = 1 - 4） Clusters

The first-principles method based on density-functional theory is used to investigate the geometries of the lowest-lying isomers of AunAg2 （n = 1 - 4） clusters. Several low-lying isomers are determined, and many of them in electronic configurations with a high spin multiplicity. The stability trend of Ag-doped Aun dusters is compared to that of pure Aun clusters. Our results indicate that the inclusion of two Ag atoms in the clusters lowers the cluster stability, indicating higher stability as the structures grow in size. The bigger energy difference between the Aun and AunAg2 curves as the structures grows in size. This information will be useful to understanding the enhanced catalytic activity and selectivity gained by using silver-doped gold catalyst.     

基于内核构建的Cu-Au-Pd团簇稳定结构优化

具有特殊催化、磁性和化学活性的三元合金团簇已成为基础科学研究的热点问题.确定其稳定结构是研究团簇性质的重要前提.针对大尺寸Cu-Au-Pd团簇结构优化,提出了内核构建的方法改进了自适应免疫优化算法的效率(称为AIOA-IC算法).采用基于紧束缚势二阶矩近似的多体Gupta势函数来描述三元合金团簇原子间相互作用.为测试算法效率优化了原子数为60的Ag-Pd-Pt团簇稳定结构.结果显示新得到的结构比文献报道的团簇结构势能量值更低,由此可知AIOA-IC算法具有更强的势能面搜索能力.运用该算法研究了38及55原子Cu-Au-Pd团簇的稳定结构.所研究的38原子Cu-Au-Pd团簇包含了五折叠、六折叠和截角八面体结构,并且原子成分比例影响了团簇的结构类型.而55原子Cu-Au-Pd团簇均为完整二十面体结构,序列参数显示Cu,Au和Pd原子分层现象明显.对于147原子Cu_(12)Au_(93)Pd_(42)团簇完整二十面体结构,中心原子为Au,内层和次外层分别被12个Cu原子和42个Pd原子占据,最外层则被92个Au原子占满.通过原子半径及表面能分析了Cu,Pd和Au原子分别倾向于分布在内层、次外层和最外层的规律.     

Dynamic Scaling of Ramified Clusters Formed on Liquid Surfaces

A comprehensive simulation model -- deposition, diffusion, rotation, reaction and aggregation model is presented to simulate the formation processes of ramified clusters on liquid surfaces, where clusters can disuse and rotate easily. The mobility （including diffusion and rotation） of clusters is related to its mass, which is given by Dm = Dos^-γD and θm = θos^-γθ, respectively. The influence of the reaction probability on the kinetics and structure formation is included in the simulation model. We concentrate on revealing dynamic scaling during ramified cluster formation. For this purpose, the time evolution of the cluster density and the weight-average cluster size as well as the cluster-size distribution scaling function at different time are determined for various conditions. The dependence of the cluster density on the deposition flux and time-dependence of fractal dimension are also investigated. The obtained results are helpful in understanding the formation of clusters or thin film growth on liquid surfaces.     

Structures,stabilities,and magnetic properties of the Fe_nAu(n=1-12) clusters

The configurations,stabilities,electronic,and magnetic properties of Fe_nAu(n = 1–12) clusters are investigated systematically by using the relativistic all-electron density functional theory with the generalized gradient approximation.The substitutional effects of Au in Fe_(n+1)(n = 1,2,4,5,10–12) clusters are found in optimized structures which keep the similar frameworks with the most stable Fe_(n+1)clusters.And the growth way for Fe_nAu(n = 6–9) clusters is that the Au atom occupies a peripheral position of Fen cluster.The peaks appear respectively at n = 6 and 9 for Fen Au clusters and at n = 5 and 10 for Fe_(n+1)clusters based on the size dependence of second-order difference of energy,implying that these clusters possess relatively high stabilities.The analysis of atomic net charge Q indicates that the charge always transfers from Fe to Au atom which causes the Au atom to be nearly non-magnetic,and the doped Au atom has little effect on the average magnetic moment of Fe atoms in Fen Au cluster.Finally,the total magnetic moment is reduced by 3 μB for each of Fen Au clusters except n = 3,11,and 12 compared with for corresponding pure Fe_(n+1) clusters.     

Transmission of low-energy (< 10 eV) O ions through Au films on TiO2(110)

In an attempt to identify the fundamental processes that influence ion transport through metallic surface layers, we have studied the transmission of O⁺ ions through discontinuous Au films adsorbed on TiO₂(110). A low energy (< 10 eV) O⁺ ion beam is generated via electron stimulated desorption when an Au-dosed TiO₂(110) substrate is bombarded with a focused 250 eV electron beam. Low energy ion scattering data indicate that Au evaporated under ultrahigh vacuum conditions at 300 K forms three-dimensional clusters on TiO₂(110). As the Au coverage increases, the formation of Au clusters on TiO₂(110) blocks a fraction of the TiO₂ surface and the O⁺ yield is attenuated. However, for high coverages (≥30% Au covered substrate) the O⁺ signal decreases at a faster rate than the TiO₂ open area fraction. We attribute the attenuation of the O⁺ yield for high Au coverages mainly to blocking of O⁺ by Au clusters, to deflection of trajectories by the image force between ions and Au clusters, and to charge transfer between desorbing O⁺ and neighboring Au clusters.     

面心立方固溶体合金的团簇加连接原子几何模型及典型工业合金成分解析

工业合金牌号的成分选择体现了固溶体合金的化学短程有序结构,满足由最近邻两层原子组成的"团簇加连接原子"模型,例如对于置换型面心立方固溶体Cu-Zn,其合金牌号成分可以表述为[Zn-Cu_(12)]Zn_(1-6)和[Zn-Cu_(12)](Cu,Zn)_6,其中方括号内为第一近邻配位多面体团簇.基于此,本文赋予团簇式以具体原子结构的含义,对置换型面心立方固溶体结构中团簇的可能存在形式进行了穷尽,得出团簇式所对应的所有"团簇加连接原子"结构单元模型,给出团簇和连接原子之间的比例和空间排列的所有可能,并对Cu-Zn和Cu-Ni合金常用牌号对应的团簇式给出了三维结构模型,进一步验证了前期关于合金团簇式解析的正确性.用这些模型中原子化学序描述合金的成分,赋予团簇式以具体的原子结构意义,为进一步开发新的合金提供了理论依据.     

WmBn(m+n≤7)团簇结构与稳定性的密度泛函理论研究

采用密度泛函理论(DFT)中的B3LYP方法,在LANL2DZ基组水平上优化W_mB_n(m+n≤7)团簇的几何结构,得到它们的基态构型,并对基态构型的平均结合能、二阶能量差分、能隙及WIB键级进行计算.结果表明:WB_n团簇的基态构型均是平面结构;当m≥2且m+n≥4时,除W₃B团簇外,其余团簇的基态结构均为立体结构;团簇的热力学稳定性随W原子个数的增加越来越好,W-W键的强度明显高于W-B和B-B键,W原子对团簇的稳定性起主导作用;W₂B₂和W₃B团簇最稳定.     

Aln(n=13–32)团簇熔化行为的分子动力学模拟研究

基于半经验的Gupta原子间多体相互作用势, 采用分子动力学方法并结合模拟退火及淬火技术, 系统研究了小尺寸铝团簇Al_n (n=13–32)的熔化行为. 模拟结果表明: 除个别尺寸(Al₁₃ 和Al₁₉) 外, 团簇熔化过程比热曲线普遍呈现杂乱无规(无明显单峰)现象, 这与实验观测小Al团簇比热普遍无规的结果完全一致. 通过分析不同温度点上团簇淬火构型的势能分布图给出了小Al团簇比热呈现无规或有规现象的成因. 对于比热无规团簇, 可以利用原子等价指数判断给出团簇熔点, 所得团簇熔点随团簇尺寸的变化趋势与实验观测结果完全一致. 关键词： Gupta势 团簇 分子动力学 熔化     

HmTiSin(m=1～2;n=2～8)团簇结构、电子性质和红外光谱的密度泛函理论研究

近些年,由于硅半导体材料在微电子工业中的潜在应用,其理论和实验研究备受人们广泛关注。尤其是过渡金属掺杂的硅团簇材料在物理化学性质方面表现了极好的稳定性。这些主要归因于过渡金属含有未填满的d轨道电子,可以填充硅团簇表面的空轨道,减少团簇表面的悬挂键,进而提高整个掺杂硅团簇的结构稳定性,同时产生各种特殊光学、磁性和超导等性质。采用密度泛函理论DFT-B3LYP方法对H_mTiSi_n(m=1～2; n=2～8)团簇的几何结构和电子性质进行了理论计算,讨论了Ti掺杂硅团簇TiSi_n(n=2～8)及其氢化团簇基态结构的变化规律、解离通道和HOMO-LUMO能隙等特征。结果表明,随着Si原子数目的增加,在TiSi_n(n=2～8)团簇中其掺杂Ti原子依次吸附在团簇的棱、面及结构内部。当在掺杂团簇表面吸附氢原子时,都优于吸附在团簇的硅原子上,而且绝大多数的氢化结构采纳了TiSi_n团簇的骨架构型。解离能和HOMO-LUMO能隙的分析结果表明在团簇表面吸附两个H原子时能够明显提高整个团簇的结构稳定性。二阶能量差分的研究发现TiSi₂和TiSi₆团簇相对其他团簇具有较高的稳定性,同时两个H₁TiSi₇和H₂TiSi₇氢化团簇的稳定性更高。此外,模拟了这些氢化团簇的红外振动特征峰,对主要特征峰进行了归属。这些研究将为过渡金属掺杂硅基团簇材料的实验制备和表征提供重要的理论参考。