利用扫描隧道显微镜表征和操纵单分子

扫描隧道显微镜（STM）提供给我们一种表征单分子的局域物理和化学特性的特殊方法，甚至还能帮助我们操纵单分子以构造分子尺度的新型器件。本文中我们采用了两种新型STM技术分别来表征封装在富勒烯笼里面的金属原子和构造一种具有较强Kondo效应的分子器件。空间dI/dV映像谱被用来探索单个Dy@C82分子中能量分辨的金属-笼杂化态，揭示了有关Dy原子在碳笼中的空间位置和Dy-碳笼之间相互作用的重要信息。我们也通过控制STM针尖诱导的高电压脉冲来诱导CoPc分子的边缘脱氢化，从而改变了这个分子在Au(111)表面的吸附构型，导致吸附在Au表面的完整CoPc分子所不具备的Kondo效应产生。     

An effective Hamiltonian for sulfur adsorption at Au(1 0 0) surface

Adsorption of sulfur at the (1 0 0) surface of gold is analyzed with the help of the density functional theory (DFT). Potential energy surface for a single S atom at the Au(1 0 0) surface is computed and a simple analytical formula was found to reproduce the ab initio results to a good accuracy. Vibration frequencies of the adsorbed S atom are computed using the harmonic approximation and the contribution of zero-point motion to the adsorption energy is evaluated. The effects of surface Au atoms relaxation in the sulfur adsorption is analyzed. The interactions between S atoms adsorbed at the nearest and the next nearest equivalent adsorption sites are computed and used to define the effective Hamiltonian describing the interactions between the adsorbed sulfur atoms.     

Surface properties of clean and Au or Pd covered hematite (α-Fe(2)O(3)) (0001)

The structure and electronic properties of different terminations of the α-Fe(2)O(3)(0001) surface were studied with spin-polarized density functional theory (DFT) and the DFT + U method accounting for the effect of strong on-site Coulomb correlations. The results for lattice relaxation, electronic and magnetic properties are presented and discussed. Though the DFT and DFT + U methods provide qualitatively very similar surface geometries they differ very much in the prediction of the electronic and magnetic properties, and the surface energetics of the clean α-Fe(2)O(3)(0001). The most stable single iron terminated (0001) surface and the oxygen-rich termination were chosen to study Au and Pd atom adsorption. The results show that both Au and Pd bind strongly to hematite surfaces and induce large changes in their geometry. The DFT + U bonding is weaker by 0.3-0.6 eV than DFT on the iron terminated surface and about 2 eV stronger on the oxygen terminated one. The binding is stronger for Pd than Au and for both adsorbates is distinctly stronger at the oxygen than at the iron terminated surface. On the iron terminated surface the adsorption binding energy per adatom increases both with Au and Pd coverage, whereas for the oxygen terminated one the opposite trend is observed.     

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     

硫在Fe(100)面吸附的第一性原理研究

基于密度泛函理论的第一性原理方法,在广义梯度近似下,计算了硫原子在Fe(100)面吸附的结构和电子性质,并计算了其分子轨道和吸附能.同时讨论了相关吸附性质与硫原子表面覆盖度(0.25-1.0ML)的关系.结果表明：硫原子吸附在H位最稳定,吸附能均随浓度的增加而单调增加;B位吸附的硫原子与Fe(100)表面的距离随浓度非单调变化,在0.5ML时达到最大,是由较高的局域电子云重叠产生的排斥作用所导致的;对比分析吸附前后硫和Fe的s及p电子的态密度,显示了硫化亚铁的生成.     

Application of thermal desorption methods in studies of catalysis: II. The oxidation of carbon monoxide on platinum

One of the major difficulties encountered in catalytic research has been the experimental characterization of the catalyst surface in its working state. Using thermal desorption techniques, we have developed a method capable of providing a quantitative measure of the concentrations of certain adsorbed reactants during catalysis. In a study of the oxidation of CO on polycrystalline platinum, three distinct reaction mechanisms have been distinguished: (1) the interaction of an oxygen molecule with a vacant Pt surface site and an adjacent adsorbed CO molecule forming a complex which dissociates to form a CO₂ molecule and an adsorbed oxygen atom; (2) the reaction between adsorbed CO and an adsorbed oxygen atom, a process in which surface transport is required to bring the reactants together; and (3) the reaction between a colliding CO molecule and an adsorbed oxygen atom. Rate constants for the reaction steps have been measured, and the active surface sites and reactive surface states on the Pt catalyst have been characterized in terms of the adsorption properties of CO.     

DFT calculations for Au adsorption onto a reduced TiO2 (110) surface with the coexistence of Cl

Residual chlorines, which originate from HAuCl₄, enhance the aggregation of gold (Au) nanoparticles and clusters, preventing the generation of highly active supported Au catalysts. However, the detailed mechanism of residual-chlorine-promoted aggregation of Au is unknown. Herein to investigate this mechanism, density functional theory (DFT) calculations of Au and Cl adsorption onto a reduced rutile TiO₂ (110) surface were performed using a generalised gradient approximation Perdew, Burke, and Ernzerhof formula (GGA–PBE) functional and plane-wave basis. Although both Au and Cl atoms prefer to mono-absorb onto oxygen defect sites, Cl atoms have a stronger absorption onto a reduced TiO₂ (110) surface, abbreviated as rTiO₂ (110) in the following, than Au atoms. Additionally, co-adsorption of a Cl atom and a Au atom or Au nanorod onto a rTiO₂ surface was investigated; Cl adsorption onto an oxygen defect site weakens the interaction between a Au atom or Au nanorod and rTiO₂ (110) surface. The calculation results suggest that the depletion of interaction between Au and rTiO₂ surface is due to strong interaction between Cl atoms at oxygen defect sites and neighbouring bridging oxygen (O^B) atoms.     

Effects of Contact Atomic Structure on Electronic Transport in Molecular Junction

Based on nonequilibrium Green＇s function and first-principles calculations, we investigate the change in molecular conductance caused by different adsorption sites with the presence of additional Au atom around the metal- molecule contact in the system that benzene sandwiched between two Au（111） leads. The motivation is the variable situations that may arise in break junction experiments. Numerical results show that the enhancement of conductance induced by the presence of additional Au is dependent on the adsorption sites of anchoring atom. When molecule is located on top site with the presence of additional Au atoms, it can increase molecular conductance remarkably and present negative differential resistance under applied bias which cannot be found in bridge and hollow sites. Furthermore, the effects of different distance between additional Au and sulfur atoms in these three adsorption sites are also discussed.     

EPR properties of Au atoms adsorbed on various sites of the MgO(1 0 0) surface from relativistic DFT calculations

Using all electron fully relativistic DFT calculations we have computed the EPR properties of Au atoms bound to various sites of the MgO surface. Changes in g-tensor and hyperfine coupling constants provide a way to identify the gold adsorption site and to map the surface morphology by comparison of measured and calculated EPR spectra. We found a strong reduction of the isotropic hyperfine coupling constant, a_iso(Au), for adsorbed gold compared to the free atom; this reduction, which is about 45% for terrace sites, is more pronounced when Au interacts with low-coordinated sites like steps, edges and corners where it is about 60%. The reduction of a_iso(Au) is accompanied by a corresponding increase of the superhyperfine interaction with the surface oxygen sites, as measured by a_iso(¹⁷O). Large anisotropies in the g-tensor are computed for all sites.     

First-principles studies: Thiolated Au2Cr and Au6Cr clusters

The structural, energetic and magnetic properties of thiol-passivating Au₂Cr and Au₆Cr clusters are investigated by performing first-principles calculation based on density functional theory. We find that the adsorption of thiolate is energetically more favorable than thiol and that the thiolates favor “top” site adsorption on Cr atom in one methanethiolate adsorbed Au₂Cr cluster while they favor “bridge” site adsorption on top of the middle point of Cr–Au bonds in three methanethiolates adsorbed Au₂Cr cluster. In thiol-passivating Au₆Cr cluster, the thiol favor “top” site adsorption on top of atom Au while the thiolate favor “bridge” site adsorption on top of the middle point of Au–Au bonds. The energetics of the reactions indicates that these thiol-passivating Au₂Cr or Au₆Cr clusters can be used as hydrogen storage materials. There are large and positive spin populations on atom Cr. The spin populations of atoms Au, S and H are attributed to both the spin delocalization and the spin polarization mechanisms.     

First-principles study of carbon atoms adsorbed on MgO(100) related to graphene growth

We have performed density functional theory calculations to understand the initial growth of graphene by studying the adsorption of carbon atoms on the oxide substrates such as magnesium oxide. For adsorption behaviors of carbon atoms on the MgO(100) surface, their adsorption geometries and binding energies are calculated. The binding of a carbon atom is the most stable at the on-top oxygen site on MgO(100). Such strong C–O binding is analyzed by examining the projected density of states. Then, we also increase the number of carbon atoms on MgO(100) to investigate their adsorption behaviors. Due to strong binding between carbon atoms, adsorbed carbon atoms form chain-like or graphene-like structures on the surface. Combined with relatively strong C–O binding, this result may explain the graphene growth on MgO(100) observed in available experiments.     

Interaction of different types of nanocages (Al12N12, Al12P12, B12N12, Be12O12, Mg12O12, Si12C12 and C24) with HCN and ClCN: DFT,TD-DFT,QTAIM, and NBO calculations

In this work, the ability of different types of nanocages including Al₁₂N₁₂, Al₁₂P₁₂, Be₁₂O₁₂, B₁₂N₁₂, Si₁₂C₁₂, Mg₁₂O₁₂ and C₂₄ for the adsorption and detection of poisonous gases HCN and ClCN has been investigated, theoretically using the D3 dispersion corrected density functional theory (DFT-D3). The absorption spectra of HCN–nanocage and ClCN–nanocage complexes were calculated by the time-dependent density functional theory (TD-DFT) and compared with the calculated absorption spectrum of isolated nanocage to investigate the ability of nanocage for sensing of HCN and ClCN gases. It was found that the strongest interaction between HCN (ClCN) molecule and nanocage takes place when the molecule is adsorbed via its N atom on the surface of nanocage except for C₂₄. Also, it was shown that the Al₁₂N₁₂ is the best adsorbent for HCN and ClCN gases among the selected nanocages and Si₁₂C₁₂ is the best sensor for the detection of these gases using the electroconductivity and absorption spectroscopy techniques.     

Liénard-type chemical oscillator

Using first-principles calculation, we have studied the properties of a series of M _x Co_1?x /Co(0001) (M = Pd, Pt) bimetallic surface alloys with atom M ratios from 0.25 to 1.0, then the effect of alloyed M metal on the properties of S adsorbed on these surfaces are discussed. Our calculations show that the alloying of metal Pd, Pt on Co(0001) weakens the S-M (M = Pd, Pt, Co) bond strength compared to monometallic surfaces and the site preference of sulfur atom is dependent on the alloyed metal M and its surface concentration. Moreover, bimetallic surface electronic structure modifications with and without sulfur are analyzed in comparison with clean Co(0001), and the correlation between the sulfur adsorption energy and the bimetallic surface d-band center is presented.     

有机铁磁界面自旋极化接触构型效应

基于第一性原理,研究了三种不同的接触构型垂直吸附在镍表面的苯双硫分子的界面自旋极化.结果表明界面自旋极化强烈依赖于接触构型,接触构型的变化可使自旋极化由正值变为负值.通过分析投影态密度,发现界面处镍原子的3d轨道与硫原子的sp³杂化轨道发生了轨道杂化.模拟机械可控断裂结实验中的界面吸附构型,根据计算的界面自旋极化,利用Julliere模型得到磁电阻约为27%,与实验测量结果较为符合.     

Adsorption and dissociation of ammonia on Au(1 1 1) surface: A density functional theory study

Periodic density functional theory (DFT) calculations using plane waves had been performed to systematically investigate the stable adsorption amine and its dehydrogenated reaction on Au(1 1 1) surface. The equilibrium configuration including on top, bridge, and hollow (fcc and hcp) sites had been determined by relaxation of the system. The adsorption both NH₃ on top site and NH₂ on bridge site is favorable on Au(1 1 1) surface, while the adsorption of NH on hollow (fcc) site is preferred. The adsorbates are adsorbed on the gold surface with the interaction between p orbital of adsorbate and the d orbital of gold atoms. The interaction between adsorbate and gold slab is more evident on the first layer than on any others. Furthermore, the dissociation reaction of NH₃ on clean gold surface, as well as on the pre-covered oxygen atom and pre-covered hydroxyl group surface had been investigated. The results show that the dehydrogenated reaction energy barrier on the pre-covered oxygen gold surface is lower. The adsorbed O can promote the dehydrogenation of amine. Additionally, OH as the product of the NH₃ dissociation reaction participates in continuous dehydrogenation reaction, and the reaction energy barrier is the lowest (22.77 kJ/mol). The results indicated that OH_ads play a key role in the dehydrogenated reaction on Au(1 1 1) surface.     

Electronic and magnetic properties of copper-family-element atom adsorbed graphene nanoribbons with zigzag edges

We have investigated the electronic and magnetic properties of copper-family-element (CFE) atom adsorbed graphene nanoribbons (GNRs) with zigzag edges using first-principles calculations based on density functional theory. We found that CFE atoms energetically prefer to be adsorbed at the edges of nanoribbons. Charges are transferred between the CFE atom and carbon atoms at the edge, which reduce the local magnetic moment of carbon atoms in the vicinity of adsorption site and change the electronic structure of GNRs. As a result, Cu adsorbed zigzag GNR is a semiconductor with energy band gap of 0.88 eV in beta-spin and energy gap of 0.22 eV in alpha-spin, while Ag adsorbed zigzag GNR and Au adsorbed zigzag GNR are both half-metallic with the energy gaps of 0.68 eV and 0.63 eV in beta-spin, respectively. These results show that CFE atom adsorbed zigzag GNRs can be applied in nanoelectronics and spintronics.     

Optoelectronic properties of two-dimensional GaN adsorbed with H,N and O: A first-principle study

In this paper, we have investigated optoelectronic properties of two-dimensional GaN adsorbed with non-metal atoms: H, N and O based on first-principle. We find that adsorption of H, N and O atom on 2D GaN is achieved by chemisorption, and the most stable adsorption site is at the top of N atom. Band structure of 2D GaN after adsorbing H atom moves to low energy region and two-dimensional GaN is transformed into an n-type semiconductor. After adsorption of N atom, a new impurity energy appears at the Fermi level, and N adatom could induce magnetism into 2D GaN. Static dielectric constants of 2D GaN increase and adsorption spectrums have extend to infrared band when adsorbing H and N. Strong reflection peaks and strong adsorption peaks after adsorption are located at deep ultraviolet range, which is beneficial for optoelectronic application in the deep ultraviolet. Specifically, two-dimensional GaN adsorbed with H atom is more conducive to manufacture of nano-optoelectronic devices.     

Pt纳米微粒自组装体系的电化学和原位FTIR反射光谱研究

用化学还原法制备了铂金属纳米微粒 ,透射电子显微镜 (TEM)表征纳米Pt微粒的平均直径为 2 5nm。通过二硫醇将Pt纳米微粒组装到多晶金电极表面。以Fe(CN) 4- 3-6 的氧化还原作为探针反应的电化学研究表明 ,Au表面组装二硫醇后抑制了电极 /溶液界面的电子传递过程 ,而在二硫醇上再组装铂纳米微粒后 ,电子传递又可进行。运用电化学FTIR反射光谱研究了Pt纳米微粒组装电极在酸性介质中CO的吸附 ,检测到CO的线型、桥式吸附态 ,分别在 2 0 30和 184 5cm- 1 附近给出红外吸收谱峰 ,并且有增强红外效应。此外 ,还观察到Pt纳米微粒上的CO孪生吸附态。红外吸收峰位于 2 10 0cm- 1 附近。     

Tailoring oxide properties: An impact on adsorption characteristics of molecules and metals

Both density functional theory calculations and numerous experimental studies demonstrate a variety of unique features in metal supported oxide films and transition metal doped simple oxides, which are markedly different from their unmodified counterparts. This review highlights, from the computational perspective, recent literature on the properties of the above mentioned surfaces and how they adsorb and activate different species, support metal aggregates, and even catalyse reactions. The adsorption of Au atoms and clusters on metal-supported MgO films are reviewed together with the cluster׳s theoretically predicted ability to activate and dissociate O₂ at the Au–MgO(100)/Ag(100) interface, as well as the impact of an interface vacancy to the binding of an Au atom. In contrast to a bulk MgO surface, an Au atom binds strongly on a metal-supported ultra-thin MgO film and becomes negatively charged. Similarly, Au clusters bind strongly on a supported MgO(100) film and are negatively charged favouring 2D planar structures. The adsorption of other metal atoms is briefly considered and compared to that of Au. Existing computational literature of adsorption and reactivity of simple molecules including O₂, CO, NO₂, and H₂O on mainly metal-supported MgO(100) films is discussed. Chemical reactions such as CO oxidation and O₂ dissociation are discussed on the bare thin MgO film and on selected Au clusters supported on MgO(100)/metal surfaces. The Au atoms at the perimeter of the cluster are responsible for catalytic activity and calculations predict that they facilitate dissociative adsorption of oxygen even at ambient conditions. The interaction of H₂O with a flat and stepped Ag-supported MgO film is summarized and compared to bulk MgO. The computational results highlight spontaneous dissociation on MgO steps. Furthermore, the impact of water coverage on adsorption and dissociation is addressed. The modifications, such as oxygen vacancies and dopants, at the oxide–metal interface and their effect on the adsorption characteristics of water and Au are summarized. Finally, more limited computational literature on transition metal (TM) doped CaO(100) and MgO(100) surfaces is presented. Again, Au is used as a probe species. Similar to metal-supported MgO films, Au binds more strongly than on undoped CaO(100) and becomes negatively charged. The discussion focuses on rationalization of Au adsorption with the help of Born–Haber cycle, which reveals that the so-called redox energy including the electron transfer from the dopant to the Au atom together with the simultaneous structural relaxation of lattice atoms is responsible for enhanced binding. In addition, adsorption energy dependence on the position and type of the dopant is summarized.     

First-principles studies of the oxygen adsorption on unreconstructed and reconstructed Ni(1 1 0) surfaces

First-principles calculations have been performed to investigate the adsorption of oxygen on unreconstructed and reconstructed Ni(1 1 0) surfaces. The energetics, structural, electronic and magnetic properties are given in detail. For oxygen adsorption on unreconstructed surface, (n×1)(n=2,3) substrate with oxygen atom on short-bridge site is found to be the most stable adsorption configuration. Whereas energetically most favorable adsorption phase of reconstructed surface is p(n×1) substrate with oxygen atom located at long-bridge site. Our calculations suggest that the surface reconstruction is induced by the oxygen adsorption. We also find there are redistributions of electronic structure and electron transfer from the substrate to adsorbate. Our calculations also indicate surface magnetic moment is enhanced on clean surfaces and oxygen atoms are magnetized weakly after oxygen adsorption. Interestingly, adsorption on unreconstructed surface does not change surface magnetic moment. However, adsorbate leads to reduction of surface magnetic moment in reconstructed system remarkably.