Electron localization determines defect formation on ceria substrates

The high performance of ceria (CeO2) as an oxygen buffer and active support for noble metals in catalysis relies on an efficient supply of lattice oxygen at reaction sites governed by oxygen vacancy formation. We used high-resolution scanning tunneling microscopy and density functional calculations to unravel the local structure of surface and subsurface oxygen vacancies on the (111) surface. Electrons left behind by released oxygen localize on cerium ions. Clusters of more than two vacancies exclusively expose these reduced cerium ions, primarily by including subsurface vacancies, which therefore play a crucial role in the process of vacancy cluster formation. These results have implications for our understanding of oxidation processes on reducible rare-earth oxides.     

"Coulomb Staircase" at Room Temperature in a Self-Assembled Molecular Nanostructure

Double-ended aryl dithiols [alpha,alpha'-xylyldithiol (XYL) and 4,4'-biphenyldithiol] formed self-assembled monolayers (SAMs) on gold(111) substrates and were used to tether nanometer-sized gold clusters deposited from a cluster beam. An ultrahigh-vacuum scanning tunneling microscope was used to image these nanostructures and to measure their current-voltage characteristics as a function of the separation between the probe tip and the metal cluster. At room temperature, when the tip was positioned over a cluster bonded to the XYL SAM, the current-voltage data showed "Coulomb staircase" behavior. These data are in good agreement with semiclassical predictions for correlated single-electron tunneling and permit estimation of the electrical resistance of a single XYL molecule (approximately18 ± 12 megohms).     

Electron-induced oxygen desorption from the TiO2(011)-2x1 surface leads to self-organized vacancies

When low-energy electrons strike a titanium dioxide surface, they may cause the desorption of surface oxygen. Oxygen vacancies that result from irradiating a TiO2(011)-2x1 surface with electrons with an energy of 300 electron volts were analyzed by scanning tunneling microscopy. The cross section for desorbing oxygen from the pristine surface was found to be 9 (+/-6) x 10(-17) square centimeters, which means that the initial electronic excitation was converted into atomic motion with a probability near unity. Once an O vacancy had formed, the desorption cross sections for its nearest and next-nearest oxygen neighbors were reduced by factors of 100 and 10, respectively. This site-specific desorption probability resulted in one-dimensional arrays of oxygen vacancies.     

Tunable field control over the binding energy of single dopants by a charged vacancy in GaAs

Local manipulation of electric fields at the atomic scale may enable new methods for quantum transport and creates new opportunities for field control of ferromagnetism and spin-based quantum information processing in semiconductors. We used a scanning tunneling microscope to position charged arsenic (As) vacancies in the gallium arsenide 110 [GaAs(110)] surface with atomic precision, thereby tuning the local electrostatic field experienced by single manganese (Mn) acceptors. The effects of this field are quantified by measuring the shift of an acceptor state within the band gap of GaAs. Experiments with varying tip-induced band-bending conditions suggest a large binding energy for surface-layer Mn, which is reduced by direct Coulomb repulsion when the As vacancy is moved nearby.     

Oxygen-mediated diffusion of oxygen vacancies on the TiO2(110) surface

Defects such as oxygen vacancies play a crucial role in the surface properties of transition metal oxides. By means of time-resolved, high-resolution scanning tunneling microscopy, we unraveled an adsorbate-mediated diffusion mechanism of oxygen vacancies on rutile TiO2(110). Adsorbed oxygen molecules mediate vacancy diffusion through the loss of an oxygen atom to a vacancy and the sequential capture of an oxygen atom from a neighboring bridging oxygen row, leading to an anisotropic oxygen vacancy diffusion pathway perpendicular to the bridging oxygen rows.     

How do small water clusters bind an excess electron?

The arrangement of water molecules around a hydrated electron has eluded explanation for more than 40 years. Here we report sharp vibrational bands for small gas-phase water cluster anions, (H2O)(4-6)- and (D2O)(4-6)-. Analysis of these bands reveals a detailed picture of the diffuse electron-binding site. The electron is closely associated with a single water molecule attached to the supporting network through a double H-bond acceptor motif. The local OH stretching bands of this molecule are dramatically distorted in the pentamer and smaller clusters because the excited vibrational levels are strongly coupled to the electron continuum. The vibration-to-electronic energy transfer rates, as revealed by line shape analysis, are mode-specific and remarkably fast, with the symmetric stretching mode surviving for less than 10 vibrational periods [50 fs in (H2O)4-].     

两个溶藻弧菌胞外多糖合成基因簇的生物信息学分析

溶藻弧菌是我国南方海水养殖最重要的病原菌之一。胞外多糖(EPSs)是细菌产生的一类具有复杂结构的多糖类物质,影响其致病性和环境适应力。基因组分析发现溶藻弧菌ZJ-51存在4个与胞外多糖合成有关的基因簇,笔者对其中2个基因簇CPS1357和CPS4543进行了生物信息学分析和实验验证。结果表明,基因簇CPS4543编码3个多糖外膜转运体系的同源蛋白Wza-Wzb-Wzc,而CPS1357编码的17个蛋白与多糖合成、转运以及调控有关。但通过染色实验、菌落形态观察和运动性分析证实这2个基因簇的缺失并不影响EPSs的合成、生物膜的形成、菌落形态及运动性。这可能是这2个基因簇在当前测试条件下受到抑制或需要特殊的环境因子诱导表达,对溶藻弧菌EPSs合成调控机制的研究,能更好地了解该病原菌在环境中的适应性。     

Interface mobility from interface random walk

Computational studies aimed at extracting interface mobilities require driving forces orders of magnitude higher than those occurring experimentally. We present a computational methodology that extracts the absolute interface mobility in the zero driving force limit by monitoring the one-dimensional random walk of the mean interface position along the interface normal. The method exploits a fluctuation-dissipation relation similar to the Stokes-Einstein relation, which relates the diffusion coefficient of this Brownian-like random walk to the interface mobility. Atomic-scale simulations of grain boundaries in model crystalline systems validate the theoretical predictions and highlight the profound effect of impurities. The generality of this technique, combined with its inherent spatiotemporal efficiency, should allow computational studies to effectively complement experiments in understanding interface kinetics in diverse material systems.     

The role of interstitial sites in the Ti3d defect state in the band gap of titania

Titanium dioxide (TiO2) has a number of uses in catalysis, photochemistry, and sensing that are linked to the reducibility of the oxide. Usually, bridging oxygen (Obr) vacancies are assumed to cause the Ti3d defect state in the band gap of rutile TiO2(110). From high-resolution scanning tunneling microscopy and photoelectron spectroscopy measurements, we propose that Ti interstitials in the near-surface region may be largely responsible for the defect state in the band gap. We argue that these donor-specific sites play a key role in and may dictate the ensuing surface chemistry, such as providing the electronic charge required for O2 adsorption and dissociation. Specifically, we identified a second O2 dissociation channel that occurs within the Ti troughs in addition to the O2 dissociation channel in O(br) vacancies. Comprehensive density functional theory calculations support these experimental observations.     

应用RAPD技术时引物数量和统计方法的研究

在研究应用RAPD技术对矮臀鳃金龟、华北大黑鳃金龟的文登种群、南京种群及东北大黑鳃金龟的分类地位时 ,采用 5、1 0、1 5、2 0、30和 36条引物的扩增谱带进行聚类分析。结果表明 ,在进行种间分类时 ,1 0条引物 ( 1 0 0条左右谱带 )便可得到稳定的树状图 ;在进行种下各阶元分类地位研究时 ,2 0条引物 ( 2 0 0条左右谱带 )即可。分别采用Nei的遗传距离 (D值 )和距离指数 (P值 )两种不同算法建立距离矩阵 ,研究结果表明 ,当引物数量足够多时 ,两种算法会得到相同的结果 ;但当引物数量较少时 ,遗传距离要优于距离指数     

In situ scanning tunneling microscopy of corrosion of silver-gold alloys

An in situ scanning tunneling microscope (STM) was used to observe the morphological changes accompanying the selective dissolution of Ag from low-Ag content Ag-Au alloys in dilute perchloric acid. This study was undertaken to explore the role of surface diffusion in alloy corrosion processes. These results are interpreted within the framework of the kink-ledge-terrace model of a crystal surface and a recent model of alloy corrosion based on a variant of percolation theory. The corrosion process leads to roughening of the surface by dissolution of Ag atoms from terrace sites. Annealing or smoothening of the surface occurs by vacancy migration through clusters and the subsequent annihilation of clusters at terrace ledges.     

Size-Specific Infrared Spectra of Benzene-(H2O)n Clusters (n = 1 through 7): Evidence for Noncyclic (H2O)n Structures

Resonant ion-dip infrared spectroscopy has been used to record size-specific infrared spectra of C(6)H(6)-(H(2)O)n clusters with n = 1 through 7 in the O-H stretch region. The O-H stretch spectra show a dramatic dependence on cluster size. For the n = 3 to 5 clusters, the transitions can be divided into three types-attributable to free, pi hydrogen-bonded, and single donor water-water O-H stretches-consistent with a C(6)H(6)-(H(2)O)n structure in which benzene is on the surface of a cyclic (H(2)O)n cluster. In n = 6 and 7 clusters, the spectra show distinct new transitions in the 3500 to 3600 wave number region. After comparison of these results with the predictions of ab initio calculations on (H(2)O)n clusters, these new transitions have been assigned to double donor O-H stretches associated with the formation of a more compact, noncyclic structure beginning with (H(2)O)(6). This is the same size cluster for which ab initio calculations predict that a changeover to noncyclic (H(2)O)n structures will occur.     

Radiation effects and oxygen vacancies in silicates

Proton and electron irradiation of silicates, minerals, and rocks produces a paramagnetic defect whose resonance spectrum is identical to that of the singly charged oxygen vacancy in silica glass and alpha-quartz. It is suggested that this defect is characteristic of all structures containing SiO(4) tetrahedra. Cracks, fracturing, and electric discharges have been observed after irradiation in planes determined by the particle ranges. These processes may contribute to the erosion materials.     

降水污染的簇分析

运用簇分析区分不同时间段降水的化学变化,将单个降水事件作为变量来分析,每次降水测量的9项主要离子指定为簇分析的观察值,簇分析完成后,保留6类簇作为描述对象.根据簇中各离子浓度的高低,将各簇概括为:氢离子簇(簇1);无特征离子簇(簇2);氯离子、钠离子簇(簇3);硫酸根、铵根离子簇(簇4);钙、镁离子簇(簇5);硝酸根、钾离子簇(簇6).显然,簇1属酸性降水簇,簇3是海洋型降水簇,簇2、5为中间过渡型,簇4、6为高离子浓度簇,强酸性降水与高离子浓度降水并不属于同一类,降水的酸性与降水中的碱性组分密切相关,降水的酸度仅当NH4+、Ca2+离子浓度尤其是NH4+离子浓度较低时才表现为强酸性.由东北季风气流和锋面系统控制的降水(簇1、2、3)是污染物经较长距离迁移造成的强酸性降水,簇4、簇5、簇6的降水受局地污染源影响,所含的离子浓度较高.     

Observation of large water-cluster anions with surface-bound excess electrons

Anionic water clusters have long been studied to infer properties of the bulk hydrated electron. We used photoelectron imaging to characterize a class of (H2O)n- and (D2O)n- cluster anions (n 相似文献   

Solid-state defect mechanism in vanadyl pyrophosphate catalysts: implications for selective oxidation

High-resolution and in situ electron microscopy of vanadyl pyrophosphate catalysts reacted in alkane (n-butane) and other reducing environments have shown evidence for surface structure modifications accompanied by two sets of symmetry-related extended defects. Defect analysis reveals that the defects are formed by pure (glide) shear mechanism. The defect mechanism suggests the presence of basal (coplanar) anion vacancies, associated with Lewis acid centers, at oxygen sites linking corner-sharing phosphorus tetrahedra and vanadyl octahedra in the active plane. These in-plane defect sites may be key to the activation of the alkane, especially in the dehydrogenation.     

Electron solvation in finite systems: femtosecond dynamics of iodide. (Water)n anion clusters

Electron solvation dynamics in photoexcited anion clusters of I-(D2O)n=4-6 and I-(H2O)4-6 were probed by using femtosecond photoelectron spectroscopy (FPES). An ultrafast pump pulse excited the anion to the cluster analog of the charge-transfer-to-solvent state seen for I- in aqueous solution. Evolution of this state was monitored by time-resolved photoelectron spectroscopy using an ultrafast probe pulse. The excited n = 4 clusters showed simple population decay, but in the n = 5 and 6 clusters the solvent molecules rearranged to stabilize and localize the excess electron, showing characteristics associated with electron solvation dynamics in bulk water. Comparison of the FPES of I-(D2O)n with I-(H2O)n indicates more rapid solvation in the H2O clusters.     

The origin of OB runaway stars

About 20% of all massive stars in the Milky Way have unusually high velocities, the origin of which has puzzled astronomers for half a century. We argue that these velocities originate from strong gravitational interactions between single stars and binaries in the centers of star clusters. The ejecting binary forms naturally during the collapse of a young (≤1 million years old) star cluster. This model replicates the key characteristics of OB runaways in our galaxy, and it explains the presence of runaway stars of ≥100 solar masses (M(⊙)) around young star clusters, such as R136 and Westerlund 2. The high proportion and the distributions in mass and velocity of runaways in the Milky Way are reproduced if the majority of massive stars are born in dense and relatively low-mass (5000 to 10,000 M(⊙)) clusters.     

蔷薇品种的数量分类学研究

本文将数量分类方法应用于蔷薇品种的分类,共选取了37个形态性状,采用SAS聚类方法,对20个蔷薇品种进行了数量分类学研究。结果表明,枝型为蔷薇品种分类的主要标准,是稳定的,作为一个比较高级的分类标准是适宜的;按照“二元分类法”原则,Q型聚类分析可以比较理想地将供试品种在Lq1=1.3948水平上分为两个系:典型藤本系、藤本系;在Lq2=1.2489水平上分为三个类:单瓣类、复瓣类和重瓣类。