Hydrogen adsorption on Pd/TiFe (110) surface

Adsorption of hydrogen on the TiFe (110) surface covered by palladium monolayer was investigated using the full potential linearized augmented plane wave method within the local density approximation. Influence of palladium coating to adsorption properties of the TiFe (110) surface as well as difference it from Pd/TiFe (100) are discussed.     

分子取向对CO在Pd(111)面吸附的影响

 用基于密度泛函理论广义梯度近似下的平面波赝势方法计算了在Pd(111)晶面两种不同CO分子取向的吸附结构。计算结果表明，CO分子碳端和氧端靠近Pd(111)面的吸附能分别为-1.75，-0.28 eV，碳端吸附的结构比氧端吸附能力强。因此，分子取向影响CO在Pd(111)面上的吸附，通过控制CO的取向可能减小Pd(111)的吸附进而减弱Pd(111)面CO分子的中毒。     

分子取向对CO在Pd(111)面吸附的影响

用基于密度泛函理论广义梯度近似下的平面波赝势方法计算了在Pd(111)晶面两种不同CO分子取向的吸附结构。计算结果表明,CO分子碳端和氧端靠近Pd(111)面的吸附能分别为-1.75,-0.28 eV,碳端吸附的结构比氧端吸附能力强。因此,分子取向影响CO在Pd(111)面上的吸附,通过控制CO的取向可能减小Pd(111)的吸附进而减弱Pd(111)面CO分子的中毒。     

Oxygen adsorption on a Pd(111) surface

The interaction of oxygen with Pd(111) has been studied by means of AES, ELS, thermal desorption (TD), electron stimulated desorption (ESD) and work function measurements. It was found that a very small part ( ～ 2–3%) of the available adsorption sites are contributing to the O⁺ electron stimulated yield, the population of the latter being accompanied by enormously large work function changes (up to ～ 0.9 eV). A mechanism of adsorption and depopulation of these sites involving oxygen bulk and surface diffusion has been proposed.     

单壁碳纳米管的场发射特性研究

利用场发射显微镜(FEM)和四极质谱计分别研究了经过热处理的单壁碳纳米管的场发射图像和热处理过程中样品脱附的残气质谱.当热处理温度达到1000℃左右时得到了单壁碳纳米管的场发射像,此像可能是顶端开口的单根(16,0)锯齿形单壁碳纳米管的具有原子可分辨的场发射图像.四极质谱分析结果表明,在此温度范围W针尖晶粒间隙中有O原子和C原子释放出来.它们对单壁碳纳米管顶端的修饰是我们能观察到这些碳纳米管场发射像的可能原因. 关键词： 单壁碳纳米管(SWCNTs) 场发射显微镜(FEM) 四极质谱     

The Formation of Pd Nanocrystals from Pd2(dba)3 Microcrystals

As‐grown platelets formed from tris‐(dibenzylideneacetone) dipalladium(0) [Pd₂(dba)₃] precursor in the presence of Pd17 RNA are investigated before and after thermal annealing. Results show that as‐grown platelets are disordered crystals of Pd₂(dba)₃ containing 1?2 nm Pd clusters and platelets grown in the absence of RNA are morphologically and structurally similar to those formed with RNA. The initially formed crystals are so sensitive to environmental variables that the degree of crystallinity can not be determined accurately by electron diffraction. X‐ray crystallography on as‐grown platelets gives a crystal structure consistent with Pd₂(dba)₃, but reveals a composition of ≈Pd_1.07(dba)₃, indicating one Pd atom in Pd₂(dba)₃ is lost from the structure. Both electron beam and thermally induced decomposition of as‐grown Pd₂(dba)₃ platelets having a hexagonal habit on the micrometer scale produces elemental Pd platelets having a hexagonal habit on the nanometer scale. These hexagonal platelets are composed of a partially sparse form of Pd₂(dba)₃ that is initially crystalline but rapidly degrades due to the loss of Pd atoms from organic ligand cages. Once released, Pd atoms aggregate to form Pd clusters, which grow and transform into well‐formed Pd nanocrystals under electron‐beam irradiation or through thermal annealing.     

H2S在Fe(100)面吸附的第一性原理研究

基于密度泛函理论第一性原理, 在广义梯度近似下, 研究了表面覆盖度为0.25 ML (monolayer)时硫化氢分子在Fe(100)面吸附的结构和电子性质, 并与单个硫原子吸附结果进行了对比. 结果表明: 硫化氢分子吸附在B2位吸附能最小为-1.23 eV, 最稳定, B1位吸附能最大为-0.01 eV, 最不稳定; 并对硫化氢分子在B1位和B2位吸附后的电子态密度进行了分析, 也表明了吸附在B2位稳定, 且吸附在B2位后硫化氢分子几何结构变化不大; 将硫化氢中硫原子吸附与单个硫原子吸附的电子性质进行了比较, 发现前者吸附作用非常微弱; 同时对吸附后的Fe(100)面进行了对比, 单个硫原子吸附的Fe(100)面电子态密度出现了一系列峰值且离散分布, 生成了硫化亚铁, 表明在硫化氢环境下, 主要是硫化氢析出的硫原子发生了吸附. 关键词： 第一性原理 Fe(100)表面 吸附能 硫化氢     

Hydrogen adsorption and diffusion on Pd(1 1 1)

The adsorption, diffusion and ordering of hydrogen on Pd(1 1 1) was studied by scanning tunneling microscopy in the temperature range of 37-90 K. At low coverage isolated hydrogen atoms were observed. They formed √3×√3-1H islands as the coverage increased. Above 1/3 monolayer (ML) coverage areas of a new phase with √3×√3-2H structure were formed, with both structures coexisting between 1/3 and 2/3 ML. Finally a 1 × 1 structure was formed after high exposures of hydrogen above 50 K, with a coverage close to 1 ML. Atomically resolved images reveal that H binds to fcc hollow sites.     

Hydrogen adsorption on Gd(0001)

The electronic structure of hydrogen adsorbate-induced states on Gd(0001) was investigated by means of photoelectron spectroscopy with linearly polarized radiation. The E vector of the incoming photon beam is rotatable. Clean and well-ordered rare-earth (0001) surfaces exhibit a highly localized surface state near the Fermi edge. After the adsorption of hydrogen, the surface state disappears and an additional sharp feature at about 4 eV binding energy is observed. For this latter state, the ratio of the radial matrix elements as well as the relative phase shifts were determined to be R=R_p/R_f=2.4±0.3 and δ_f−δ_p=310±10°, respectively. The removal of the Gd surface state by hydrogen adsorption was investigated by means of scanning tunneling microscopy (STM) and spectroscopy (STS). The removal of the surface state exhibits domain-like behavior, with surface steps acting as domain boundaries. The tunneling spectra reveal that hydrogen adsorption causes a dramatic reduction in the differential conductivity near the Fermi level.     

Cu(100)表面c(2×2)-N原子结构与吸附行为研究

用密度泛函理论的总能计算研究了金属铜(100)面的表面原子结构以及氮原子的c(2×2)吸附状态.研究结果表明：在Cu(100) c(2×2)-N表面系统中，氮原子处于四度配位的空洞(FFH)位置，距离最表面铜原子层的垂直距离为0.20?，最短的Cu—N键长度为1.83?.结构优化的计算否定了被吸附物导致的表面再构模型，即c(2×2)元胞的两个铜原子在垂直于表面方向发生相对位移，一个铜原子运动到氮原子之上的模型.该吸附表面的功函数约为4.65eV, 氮原子的平均吸附能为4.92 eV(以孤立氮原子为能量参考点).计算结果还说明，Cu—N杂化形成的表面局域态的位置在费米面以下约1.0 eV附近出现，氮原子和第一层以及第二层铜原子均有不同程度的杂化作用.该结果为最近有关该表面的STM图像的争论提供了判据性的第一性原理计算结果. 关键词： Cu(100) c(2×2)-N 表面吸附态 密度泛函总能计算     

Formation of single layer h-BN on Pd(1 1 1)

The structure of hexagonal boron nitride (h-BN) on Pd(1 1 1) was studied with low energy electron diffraction (LEED), photoelectron spectroscopy and scanning tunnelling microscopy (STM). h-BN forms flat monolayers on the Pd(1 1 1) surface in contrast to Rh(1 1 1) where a complex self-assembled double layer structure, the nanomesh [M. Corso, W. Auwärter, M. Muntwiler, A. Tamai, T. Greber, J. Osterwalder, Science 303 (2004) 217], appears. The LEED patterns reveal a dominating 10 × 10 h-BN superstructure, with a second, distinct structure rotated by 30° and further azimuthally randomly oriented h-BN overlayers. This is consistent with STM images which show several different Moiré patterns associated with different rotation angles of the overlayer. Additionally the use of thin Pd(1 1 1) films instead of single crystal substrates was studied. No significant differences in the h-BN film quality were found.     

Pd, Co and Co-Pd clusters on the ordered alumina film on NiAl(1 1 0): Contact angle, surface structure and composition

We have investigated the structure and morphology of Co and Pd clusters grown at room temperature on an alumina film on NiAl(1 1 0) by scanning tunneling microscopy, low energy ion scattering and Auger electron spectroscopy. We have also studied the clusters after annealing to 300 °C and Pd clusters deposited at 300 °C. Mixed Co-Pd clusters obtained by sequential deposition at room temperature were also studied. Pure Co deposited at room temperature forms a single type of clusters, most or all of them with close-packed planes parallel to the oxide surface. Their shape can be approximated by truncated spheres with a high contact angle of 115-125°. These clusters are stable upon annealing up to 300 °C.Pd clusters deposited at room temperature grow in two different modes. At the reflection domain boundaries the clusters grow in their thermodynamically favorable shape. The clusters do not have a single crystallographic orientation and their shape can be approximated by a truncated sphere with a high contact angle of about 110°, especially at very low coverages (below 0.05 ML). At the antiphase domain boundaries, the Pd clusters grow in (1 1 1) orientation and on some of them small (1 1 1) facets appear at their tops already at low coverages. For higher coverages of Pd, the majority of Pd clusters are rather flat with a large Pd(1 1 1) facet on top. The clusters’ shape at the antiphase domain boundaries differs from the thermodynamically favorable one, due to kinetic limitations, especially at higher coverages. Annealing the Pd clusters to 300 °C leads to re-structuring of these Pd clusters. They transform into higher and more rounded clusters and a thin disordered alumina film is formed on top of the clusters. When Pd is deposited at 300 °C, about 16% of the Pd clusters have a steep slope and rounded tops. The rest of the Pd forms lower clusters, goes subsurface and is covered by a disordered alumina film. When Co and Pd are deposited sequentially, Pd covers the Co clusters forming a shell. The resulting mixed clusters are still truncated spheres with a lowered contact angle. For deposition in the reverse order (first Pd and then Co) we found that Co forms an alloy with Pd already at room temperature.     

MoSi_2(001)表面的氧吸附行为

运用第一原理密度泛函理论方法,首先计算了MoSi_2各清洁表面的表面能,(001)Si-|-Si断面具有较低的表面能,是MoSi_2最可能的解理面;通过生成能及键布居分析研究了单氧原子、双氧原子及氧分子在(001)Si-|-Si断面的吸附行为,发现单氧原子在空位处吸附最稳定,此时O极易与Si结合,得到的Si-O-Si键长及键角与SiO_2的非常接近,表明低浓度下O极易与表面的Si结合生成SiO_2;双氧原子发生空位+顶位吸附时O原子除与Si有强作用外,可与Mo有一定相互作用;氧分子以平行的方式接近空位最有利于吸附,此时氧分子最易分解为氧原子,发生氧原子在空位的吸附.     

Pu(100)表面吸附CO2的密度泛函研究

采用广义梯度密度泛函理论的改进Perdew-Burke-Ernzerh方法结合周期性层晶模型,研究了CO₂分子在Pu（100）面上的吸附和解离.吸附能和几何构型的计算表明,CO₂以穴位C4O4构型吸附最为有利,吸附能为1.48 eV.布居分析和态密度分析表明,CO₂与Pu表面相互作用的本质主要是CO₂分子的杂化轨道2π_μ与Pu5f,Pu6d,Pu7s轨道通过强电子转移和弱重叠杂化的方式相互作用而生成了新的化学键.计算的CO₂→CO+O解离能垒为0.66 eV,解离吸附能为2.65 eV, 表明在一定热激活条件下CO₂分子倾向于发生解离性吸附.O₂,H₂,CO和CO₂在Pu （100）面吸附的比较分析表明,较低温度下的吸附强度顺序依次为O₂,CO,CO₂,H₂;较高温度下的吸附强度顺序依次为O₂,CO₂,CO,H₂. 关键词： 密度泛函理论 Pu （100） 2')" href="#">CO₂ 吸附和解离     

Hydrogen adsorption on the silicon (001) surface and on a step on the (111) surface

Adsorption of atomic hydrogen on an ideal (001) silicon surface is investigated in the present paper. Saturation of one of the two dangling bonds of a silicon atom on this surface by hydrogen removes the interaction (hybridization) between them, resulting in the appearance of a bonding and an antibonding chemisorption state associated with the attacked dangling bond, and in the shift of the peak of the remaining unsaturated dangling bond to the energy typical of a surface state of the (111) surface. Further saturation leads to the disappearance of this peak from the energy spectrum. An analogous situation occurs for the silicon atom with two dangling bonds on a step on the (111) surface, when hydrogen is chemisorbed. Both examples testify to the local chemical nature of Shockley surface states in silicon.The authors thank A. N. Sorokin for useful discussions.     

Water adsorption on the Be(0001) surface: from monomer to trimer adsorption

In this paper, the density functional theory has been used to perform a comparative theoretical study of water monomer, dimer, trimer, and bilayer adsorptions on the Be(0001) surface. In our calculations, the adsorbed water molecules are energetically favoured adsorbed on the atop sites, and the dimer adsorption is found to be the most stable with a peak adsorption energy of ～437 meV. Further analyses have revealed that the essential bonding interaction between the water monomer and the metal substrate is the hybridization of the water 3a₁-like molecular orbital with the (s, p_z) orbitals of the surface beryllium atoms. While in the case of the water dimer adsorption, the 1b₁-like orbital of the H₂O molecule plays a dominant role.     

三氧化钨表面氢吸附机理的第一性原理研究

采用基于密度泛函理论的第一性原理平面波超软赝势方法,在广义梯度近似下,研究了立方WO_3,WO_3(001)表面结构及其氢吸附机理.计算结果表明立方晶体WO_3理论带隙宽度为0.587 eV.WO_3(001)表面有WO终止(001)表面和O终止(001)表面两种结构,表面结构优化后W—O键长和W—O—W键角改变,从而实现表面弛豫;WO终止(001)表面和O终止(001)表面分别呈现n型半导体特征和p型半导体特征.分别计算了H原子吸附在WO终止(001)表面和O终止(001)表面的H—O_(2c)—H,H—O_(2c)…H—O_(2c),H—O_(1c)—H和H—O_(1c)…H—O_(1c)四种吸附构型,其中H—O_(1c)—H吸附构型的吸附能最小,H—O键最短,H失去电子数最多,分别为-3.684 eV,0.0968 nm和0.55e,此吸附构型最稳定.分析其吸附前后的态密度,带隙从吸附前的0.624 eV增加到1.004 eV,价带宽度基本不变.H的1s轨道电子与O的2p,2s轨道电子相互作用,在-8和-20 eV附近各形成了一个较强的孤立电子峰,两个H原子分别与一个O_(1c)原子形成化学键,最终吸附反应生成了一个H_2O分子,同时产生了一个表面氧空位.     

Hydrogen adsorption on Pt-decorated closed-end armchair (3,3), (4,4) and (5,5) single-walled carbon nanotubes

ABSTRACT

Structures of small lengths of capped (3,3), (4,4) and (5,5) single-walled carbon nanotubes (SWCNTs) and their structures decorated by Pt atom and Pt_n clusters (n = 2–4) were obtained using density functional theory calculations. Binding abilities of Pt atom and Pt_n clusters on the outer surface of SWCNTs at various adsorption sites were explored. Adsorptions of H₂ onto Pt atom of the Pt-decorated (3,3), (4,4) and (5,5) SWCNTs were studied and their adsorption energies are reported. The thermodynamic properties and equilibrium constants for H₂ adsorptions on the Pt₄-decorated (3,3), (4,4) and (5,5) SWCNTs were obtained. The adsorption of H₂ on the Pt atom of the Pt₄/(3,3) SWCNT was found to be the most preferred reaction of which enthalpy and free energy changes at room temperature are ?46.61 and ?23.99 kcal/mol, respectively.     

Si(111)-(7×7)表面上Ge量子点的自组织生长

用扫描隧道显微镜研究了Si(111)(7×7)表面上Ge量子点的自组织生长.室温下用固相外延法在硅基底上沉积亚单层的Ge,然后在适当的温度下退火可以聚集形成有序的Ge量子点.由于Ge在Si(111)(7×7)表面选择性的吸附而形成有序的Ge量子点. 关键词： 锗 硅 扫描隧道显微镜 自组织生长