Binding sites for cluster atoms: Ir on Ir(111)

Clusters of indium atoms on iridium (111) have been examined with the field ion microscope. From observations on highly symmetrical trimers, tetramers, and heptamers it appears that in larger clusters the atoms prefer to sit in bulk (fcc) sites, even though single adatoms favor surface (hcp) sites. These larger clusters thus serve to continue the normal fcc structure.     

氯原子在Cu(111)表面的吸附结构和电子态

密度泛函理论(DFT)总能计算研究了不同覆盖度下氯原子在Cu(111)表面的吸附结构和表面电子态。计算结果表明,清洁Cu(111)表面自由能 为15.72 ,表面功函数φ为4.753eV。在1/4ML和1/3ML覆盖度下,每个氯原子在Cu(111)表面fcc谷位的吸附能分别等于3.278eV/atom和3.284eV/atom。在1/2ML覆盖度下,两个紧邻氯原子分别吸附于fcc和hcp谷位,氯原子的平均吸附能为2.631eV/atom。在1/3ML覆盖度下,fcc和hcp两个位置每个氯原子吸附能的差值约为2meV/atom,与正入射X光驻波实验结合蒙特卡罗方法得到结果(<10meV/atom)基本一致。在1/4ML、1/3ML和1/2ML覆盖度下,吸附后Cu(111)表面的功函数依次为5.263eV、5.275eV和5.851eV。吸附原子和衬底价轨道杂化形成的局域表面电子态位于费米能级以下约1.2eV、3.6eV和4.5eV等处。吸附能和电子结构的计算结果表明,氯原子间的直接作用和表面铜原子紧邻氯原子数目是决定表面结构的两个重要因素。     

Stacking-fault nucleation on Ir(111)

Variable temperature scanning tunneling microscopy experiments reveal that in Ir(111) homoepitaxy islands nucleate and grow both in the regular fcc stacking and in the faulted hcp stacking. Analysis of this effect in dependence on deposition temperature leads to an atomistic model of stacking-fault formation: The large, metastable stacking-fault islands grow by sufficiently fast addition of adatoms to small mobile adatom clusters which occupy in thermal equilibrium the hcp sites with a significant probability. Using parameters derived independently by field ion microscopy, the model accurately describes the results for Ir(111) and is expected to be valid also for other surfaces.     

Site determination and thermally assisted tunneling in homogenous nucleation

A combined low-temperature scanning tunneling microscopy and density functional theory study on the binding and diffusion of copper monomers, dimers, and trimers adsorbed on Cu(111) is presented. Whereas atoms in trimers are found in fcc sites only, monomers as well as atoms in dimers can occupy the fcc as well as the metastable hcp site. In fact the dimer fcc-hcp configuration is only 1.3 meV less favorable with respect to the fcc-fcc configuration. This enables a confined intracell dimer motion, which at temperatures below 5 K is dominated by thermally assisted tunneling.     

Cl原子在γ-TiAl(111)表面吸附的第一性原理研究

基于密度泛函理论,在广义梯度近似下研究了Cl在γ-TiAl(111)表面的吸附.计算结果表明:γ-TiAl(111)表面的面心立方位置(fcc)和六角密排位置(hcp)为Cl吸附的稳定位置,当覆盖度Θ小于一个单层(ML)时,Cl原子倾向于吸附在γ-TiAl(111)表面近邻为多Ti的位置.电子结构分析发现,Cl原子同表面金属原子形成较强的离子键,并且成键具有一定的方向性.当Cl原子和O原子共同在γ-TiAl(111)表面吸附时,二者都趋     

Electrodeposited cobalt films: hcp versus fcc nanostructuring and magnetic properties

The crystallographic structure and morphology of electrodeposited cobalt films on Au(111) is found to be very sensitive on the electrolyte pH value and on the overpotential applied during deposition. The samples, 2 to 500 nm thick, where characterized by nuclear magnetic resonance (NMR), atomic force microscopy (AFM) and electron diffraction. The latter technique shows that the Co films grow in registry with the gold underlayer, reproducing the Au(111) texture. During the first stage of growth and depending on overpotential and pH value, either continuous hcp Co films or hcp Co islands are formed. Only the latter growth mode leads to an out of plane magnetization with 100% of remanence. Increasing the thickness, fcc Co becomes the prevailing phase. Eventually the fcc to hcp ratio saturates at the same value regardless the overpotential. The thickness for which the equilibrium fcc to hcp ratio is obtained as well as the sample structure and morphology before saturation, depend strongly on the overpotential value. In any case, the predominance of the fcc Co phase leads to an in plane magnetization of the thick samples. This study opens up new opportunities of engineering the properties of electrodeposited cobalt films. Received 29 February 2000 and Received in final form 3 July 2000     

Al吸附在Pt,Ir和Au的(111)面的低覆盖度研究

应用密度泛函理论,系统研究了Al原子在Pt(111),Ir(111)和Au(111)表面的桥位、顶位、三重面心立方(fcc)洞位和六角密排(hcp)洞位这四个典型位置的吸附情况. 主要计算了三吸附体系的几何结构、平均结合能和差分电荷密度,并系统讨论了相关原子的密立根电荷布居数和投影态密度.研究发现,对于Pt(111)和Ir(111)表面,Al原子在hcp洞位最稳定,但是对于Au(111)表面,Al原子在fcc洞位最稳定. 关键词： 吸附 密度泛函理论 结合能 电子结构     

合成氨钌催化剂的晶体和形貌敏感性

哈伯-博施法合成氨反应是高温高压的耗能过程,因此降低该过程的能量消耗及开发温和条件下合成氨反应催化剂具有重要意义. 金属钌是合成氨反应中最有前途的催化剂之一,一直备受广泛关注. 确定金属钌催化剂的结构敏感性并提高其比质量活性是多相催化中亟待解决的重要问题. 氮气(N₂)活化是合成氨反应中的关键步骤. 本文通过第一性原理理论计算和微观动力学模拟方法系统研究了具有六方密排和面心立方晶体结构的钌催化剂上N₂活化过程和N₂解离反应速率. 理论计算研究表明,在六方密排Ru形貌中,{2130}晶面具有最高的N₂解离活性,其次是{0001}台阶面,它们比六方密排Ru其他表面上N₂解离反应速率高3个数量级以上;在面心立方Ru形貌中,{211}和{311}表面上N₂解离活性最高. 这些结果都表明台阶面/台阶位对氮气活化至关重要. 虽然六方密排Ru {2130}晶面具有最低的N₂解离能垒,然而由于面心立方Ru上可以暴露更高密度的活性位点,使得面心立方Ru比六方密排Ru具有更高的N₂转化速率. 本研究深入理解了N₂解离过程中,金属Ru 催化剂形貌和晶相结构敏感性,这为设计和优化高活性的合成氨Ru催化剂提供了理论基础.     

Stacking faults in ultra-thin films of silver on Al(111) investigated by medium energy ion scattering

Medium energy ion scattering has been used to investigate depositions of 0.2, 1.4, 3.5 and 4.8 ML of silver onto Al(111). Energy profiles indicate alloying to the extent that aluminium is still visible after the deposition of 4.8 ML. From assessments of the visibility, blocking dips and fits using VEGAS simulations it is shown that the first two layers continue the fcc stacking but after that hcp and fcc twin-type stacking faults occur. The 1.4 ML structure is consistent with a mixed structure of 85% fcc and 15% hcp indicating that some silver occupies a third layer. The blocking curve from the structure formed by 3.5 ML equivalent deposition can be simulated by 56% fcc, 32% hcp and 12% fcc twin and that from 4.8 ML by 59% fcc, 23% hcp and 18% fcc twin. This provides direct evidence of the incidence of hcp stacking when silver is deposited onto Al(111) in the range between 2 and 5 ML.     

Diffusion of atoms on an fcc(111) surface

The motion of adatoms on an fcc(111) surface is modeled. In light of recently revealed specific features of the potential energy surface, a new empirical potential taking into account the nonequivalence of fcc and hcp adsorption sites was proposed. The modeling was performed by the method of stochastic cycles, a new variety of MDM. Calculations were performed for the diffusion of oxygen atoms over a platinum surface. The potential energy surface was constructed based on experimental data and DFT calculations. An analysis demonstrated that the diffusion activation energy coincides with the static barrier while the preexponential factor is weakly temperature-dependent. Note, however, that the degree of asymmetry of the potential produces a significant effect on the preexponential factor: the changeover from a symmetric two-well potential to a strongly asymmetric single-well potential causes an increase in the preexponential factor by an order of magnitude.     

C_2H_x(x=4～6)在Ni(111)表面吸附的DFT研究

采用密度泛函理论与周期平板模型相结合的方法,对物种C_2H_x(x=4～6)在Ni(111)表面的top,fcc,hcp和bridge位的吸附模型进行了结构优化、能量计算,得到了各物种较有利的吸附位;并对最佳吸附位进行密立根电荷和总态密度分析.结果表明:C_2H_6和C_2H_4在Ni(111)表面的最稳定吸附位都是top位,吸附能分别是-36.41和-48.62 kJ·mol~(-1),物种与金属表面吸附较弱;而C_2H_5在Ni(111)表面的最稳定吸附位hcp的吸附能是-100.21 kJ·mol~(-1),物种与金属表面较强;三物种与金属表面之间都有电荷转移,属于化学吸附.     

The structure of an Fe monolayer on the Ni (111) surface. A density-functional study using the generalized gradient approximation

Using a density-functional method that employs linear combinations of atomic orbitals as basis sets, nonlocal norm-conserving pseudopotentials and the generalized gradient approximation for exchange and correlation, we found that at 0 K the atoms of an Fe monolayer on the Ni (111) surface occupy hcp rather than fcc sites, in keeping with previous predictions made using the ab initio all-electron full-potential linearized augmented plane wave method with the local spin density approximation.     

铝和银在铱（111）宽范围吸附的稳定性、原子构型及电子特性研究

利用第一性原理密度泛函理论研究了铝和银在铱的111面的宽范围吸附特性。基于密度泛函理论计算了覆盖度在0.11ML到2.00ML的结构稳定性、原子构型及平均结合能。对于铝原子在铱111面的吸附,最稳定的结构是铝原子覆盖度为0.5ML位于密堆六方空位（hcp-hollow）,相应的结合能为-4.68eV;对于亚层铝原子的吸附,最稳定结构是铝原子覆盖度为1.00ML时位于octahedral位置,相应的结合能为-5.28eV。对于覆盖度为2.00ML的满覆盖度混合结构的表层及亚层吸附,最稳定结构是Al位于六方密堆及八方密堆位置,相应的结合能为-4.70eV。这意味着当铝原子以满覆盖度吸附在铱的111面上时,趋向于在铱的111面的亚层形成化学键,而非吸附于表层。相比于铝吸附在铱111面,银的吸附特性呈现出很大的不同,面心位置更为稳定,在覆盖度为0.25ML时其结合能为3.89eV,略微高出密堆六方位置处3.88eV的结合能。     

铝和银在铱（111）宽范围吸附的稳定性、原子构型及电子特性研究

利用第一性原理密度泛函理论研究了铝和银在铱的111面的宽范围吸附特性。基于密度泛函理论计算了覆盖度在0.11ML到2.00ML的结构稳定性、原子构型及平均结合能。对于铝原子在铱111面的吸附,最稳定的结构是铝原子覆盖度为0.5ML位于密堆六方空位（hcp-hollow）,相应的结合能为-4.68eV;对于亚层铝原子的吸附,最稳定结构是铝原子覆盖度为1.00ML时位于octahedral位置,相应的结合能为-5.28eV。对于覆盖度为2.00ML的满覆盖度混合结构的表层及亚层吸附,最稳定结构是Al位于六方密堆及八方密堆位置,相应的结合能为-4.70eV。这意味着当铝原子以满覆盖度吸附在铱的111面上时,趋向于在铱的111面的亚层形成化学键,而非吸附于表层。相比于铝吸附在铱111面,银的吸附特性呈现出很大的不同,面心位置更为稳定,在覆盖度为0.25ML时其结合能为3.89eV,略微高出密堆六方位置处3.88eV的结合能。     

Controlled low-temperature molecular manipulation of sexiphenyl molecules on Ag111 using scanning tunneling microscopy

A novel scanning tunneling microscope manipulation scheme for a controlled molecular transport of weakly adsorbed molecules is demonstrated. Single sexiphenyl molecules adsorbed on a Ag(111) surface at 6 K are shot towards single silver atoms by excitation with the tip. To achieve atomically straight shooting paths, an electron resonator consisting of linear standing-wave fronts is constructed. The sexiphenyl manipulation signals reveal a pi ring flipping as the molecule moves from the hcp to fcc site. Ab initio calculations show an incorporation of the Ag atom below the center of a pi ring.     

Ab-initio study of the coadsorption of Li and H on Pt(001), Pt(110) and Pt(111) surfaces

The coadsorption of Li and H atoms on Pt(001), Pt(110) and Pt(111) surfaces is studied using density functional theory with generalised gradient approximation. In all calculations Li, H and the two topmost layers of the metal were allowed to relax. At coverage of 0.25 mono-layer in a p(2×2) unit cell, lithium adsorption at the hollow site for the three surfaces is favoured over top and bridge sites. The most favoured adsorption sites for H atom on the Pt(001) and Pt(110) surfaces are the top and bridge sites, while on Pt(111) surface the fcc site appears to be slightly favoured over the hcp site. The coadsorption of Li and atomic hydrogen shows that the interaction between the two adsorbates is stabilising when they are far from each other. The analysis of Li, H and Pt local density of states shows that Li strongly interacts with the Pt surfaces.     

Lineshapes in quasi-elastic scattering from species hopping between non-equivalent surface sites

We present an analytic model applied to quasi-elastic scattering from an adsorbed surface species undergoing jump diffusion between adsorption sites described by a Bravais lattice combined with a basis of multiple points. The model allows for hops between adsorption sites which are both symmetrically and energetically inequivalent. We give results for 1-D hopping, which are applicable to a species jumping between the top and bridge sites along the [11?0] direction on an fcc-(110) surface or for jumps along a step edge. In 2-D, results for hopping between fcc and hcp hollow sites and between the bridge sites of an fcc-(111) surface are presented. These examples give characteristic signatures which will allow these forms of motion to be recognized in experimental data and will enable the underlying physical parameters to be extracted by comparison with the analytical forms derived here.     

AlN/NbN纳米结构多层膜的共格异结构外延生长研究

采用射频磁控溅射法制备了NbN,AlN单层膜及不同调制周期的AlN/NbN纳米结构多层膜,采用X射线衍射仪、小角度X射线反射仪和高分辨透射电子显微镜等对薄膜进行了表征.结果表明：单层膜AlN为六方结构,NbN为面心立方结构;AlN/NbN多层膜中AlN为六方结构,NbN为面心立方结构,界面处呈共格状态,其共格关系为c-NbN（111）面平行于h-AlN（0002）面,晶格错配度为013%.热力学计算表明:AlN/NbN多层膜中不论AlN层与NbN层的厚度如何,AlN层均不会形成亚稳的立方AlN,而是形成 关键词： AlN/NbN纳米结构多层膜 共格外延生长 异结构     

Crystal structure of solid C70

Detailed analysis of the room temperature X-ray powder diffraction data of pure solid C₇₀ is reported. C₇₀ prepared by slow evaporation from toluene solution adopts an hcp structure (space groupP6₃/mmc) witha=10·53(1) A andc=17·24(1) A. C₇₀ sublimed on to Si wafer adopts an fcc structure witha=14·89(1) A. The occurrence of both the hcp and fcc phases is rationalized in terms of cohesive energy calculations. Theoretical calculations of the diffraction pattern for the hcp structure, taking into account (a) orientational disorder amongst the molecules (b) presence of stacking faults and (c) a fraction of the sample to be amorphous/microcrystalline is seen to provide very good agreement with the experimental diffraction pattern.     

Critical point energies in hcp and fcc cobalt from appearance potential spectra

Appearance potential spectra have been measured for (low-temperature) hcp and (high-temperature) fcc cobalt. The measurements allowed a determination of the transition temperatures of (690±6) K for the hcp fcc transition and (653±12) K for the fcc hcp transition in good agreement with earlier findings. Critical-point energies are (6.7±0.3) eV for the M point in hcp cobalt and (5.6±0.3) eV for the L₇ and (8.9±0.3) eV for the X₇, K₈ critical points in fcc cobalt, respectively.