Field emission properties of capped carbon nanotubes doped by alkali metals:a theoretical investigation

The electronic structures and field emission properties of capped CNT55 systems with or without alkali metal atom adsorption were systematically investigated by density functional theory calculation.The results indicate that the adsorption of alkali metal on the center site of a CNT tip is energetically favorable.In addition,the adsorption energies increase with the introduction of the electric field.The excessive negative charges on CNT tips make electron emittance much easier and result in a decrease in work function.Furthermore,the inducing effect by positively charged alkali metal atoms can be reasonably considered as the dominant reason for the improvement in field emission properties.     

Anisotropy of the work function change in physical adsorption

Smoluchowski's concept of the surface double layer of bare metals is extended for physical adsorption of rare gas atoms on metal surfaces. With the use of the polarization approach it is possible to show that the work function decrease on physical adsorption of rare gases is anisotropic. A simple rule is suggested according to which the work function change produced by physical adsorption of the given rare gas on different crystal faces of the same metal [-Δφ(hkl)] decreases with increasing work function of the bare face [φ₀(hkl)] and/or with increasing packing density of the bare face. The former correlation is quantitative, whereas the latter correlation is only qualitative. The above predictions are compared with the first data available in the literature.     

Inelastic processes in the scattering of metastable rare gas atoms at metal surfaces

Electron spectra of various metastable rare gas atoms systematically measured on a Pt(111) surface with Rb coverages ranging from submonolayers (3%) to multilayers are presented. The different decay channels of the excited particles are discussed in terms of resonant electron exchange processes between the substrate and the projectile in relation to the work function. It is shown that below a certain value of the work function a highly excited negative rare gas atom is formed which can undergo different de-excitation processes. A careful discussion of the branching ratios into the decay channels offers a natural explanation of the variations in the electron spectra induced by alkali metal adsorption. Additionally, an attempt is made to extract information about the alkali metal chemisorption state from the observed electron spectra.     

第一性原理研究氧在Ni(111)表面上的吸附能及功函数

采用基于密度泛函理论（DFT）广义梯度近似（GGA）下的第一性原理方法系统地研究了不同覆盖度下O在Ni（111）表面的吸附特性.计算结果表明,O在Ni（111）表面的稳定吸附位为三重面心立方（fcc）洞位,吸附能随着覆盖度的增加而减小,O诱导Ni（111）表面功函数的变化量与覆盖度成近线性关系,并随着覆盖度的增加而增大.同时,通过对电子密度和分波态密度的分析发现：O在Ni（111）表面的吸附使得Ni表面电子向O原子转移,形成表面偶极矩,导致功函数增加;表面Ni原子的3d轨道和O的2p轨道通过耦合、杂化作用形成成键态和反键态,而反键态几乎不被占据,因而O—Ni键相互作用比较强,吸附能较大. 关键词： 表面吸附 密度泛函理论 吸附能 功函数     

Calculation of the temperature-dependent energy characteristics of adsorption systems based on transition metals

Self-consistent calculations of the temperature-dependent absorption energy and electron work function on the surface of absorption systems based on transition metals have been performed via the electron-density functional method. The influence of substrate surface relaxation on the energy characteristics of adsorption systems is investigated. Gradient corrections to kinetic and exchange-correlation energies are estimated to describe a strong inhomogeneity arising in the electron system of the subsurface region. The influence of electron-ion interaction on energy characteristics is calculated with the use of the Ashcroft pseudopotential. The temperature-dependent formation of various adsorption structures from transition metal atoms is discussed.     

A first-principles study on the interaction of CO molecules with VIII transition metals-embedded graphitic carbon nitride as an excellent candidate for CO sensor

We studied the adsorption behavior of CO molecules over graphitic carbon nitride (gCN) and VIII transition metals (TM)-embedded gCN systems (TM=Ni, Pd, and Pt atoms) using density functional theory. The results indicated that the Pt-embedded gCN is excellent candidate for adsorption of CO molecules with adsorption energy of −2.77 eV, which is much better than those of the other adsorbents. Furthermore, it was observed that the band gap energies of TM-embedded systems were less than that of pristine gCN and decoration of transition metal atoms leads to the formation of mid gap impurity states, resulting in increase of electrical conductivity. Additionally, the Lowdin charges displayed that upon adsorption of CO molecules, this molecule acts as an electron acceptor and gCN systems behave as an electron donor with electron transfer from d-orbitals of transition metal atoms to the states of CO molecule. The results of spin polarized band structure indicated that the pristine gCN, Ni and Pd-embedded systems are non-magnetic, whereas Pt-embedded gCN induces non-zero magnetic moment equal to 1.35 μB. Therefore, our results revealed that among the TM-embedded systems, Pt-embedded gCN is more effective than those of the other adsorbents in sensing and removing of this gas from the atmosphere.     

Field adsorption of helium and neon on metals: an integrated theory

Density functional theory has been used to carry out self-consistent calculations relating to the field adsorption of helium and neon on metal surfaces. The transition from physisorption in low electric fields to field-induced chemisorption in high electric fields is explicitly demonstrated with electron density maps. The higher binding energies of rare gases above protruding metal surface atoms are explained as resulting from local field enhancement, and an approximate formula for the helium-on-tungsten system is derived that gives the total short-range field-adsorption binding energy as a function of the external field and a local field-enhancement factor. A survey of earlier theoretical approaches to rare-gas adsorption in electric fields is included. The present treatment can be regarded as an integrated theory in which both covalent and polarisation effects have their place; it brings out the role of polarisation contributions to the total binding energy, and allows us to clarify the relationship between the earlier classical models and the present quantum theory of field-induced chemisorption.     

卷曲方式对Rh原子在单壁碳纳米管内外吸附的影响

碳纳米管曲率与卷曲方式是同时存在并影响金属原子在碳纳米管内外吸附行为的重要因素, 单独研究卷曲方式对金属吸附行为的影响较困难. 选取曲率相近、卷曲方式不同的扶手椅型(6, 6)、锯齿型(10, 0)与手性(8, 4)单壁碳纳米管(SWCNT), 利用密度泛函理论研究了Rh原子在SWCNT内外的吸附行为. 构型优化表明:由于SWCNT卷曲方式不同, 导致Rh原子在(6, 6),(10, 0)与(8, 4)SWCNT内外吸附的稳定构型不同; 不同卷曲方式亦使SWCNT与Rh原子相互作用的C原子不同, 导致Rh 关键词： 密度泛函理论 单壁碳纳米管 Rh原子 卷曲方式     

金属原子修饰石墨烯体系催化性能的理论研究

采用基于密度泛函理论的第一性原理方法研究了单个CO和O2气体分子在金属原子修饰石墨烯表面的吸附和反应过程.结果表明:空位缺陷结构的石墨烯能够提高金属原子的稳定性,金属原子掺杂的石墨烯体系能够调控气体分子的吸附特性.通入混合的CO和O2作为反应气体,石墨烯表面容易被吸附性更强的O2分子占据,进而防止催化剂的CO中毒.此外,对比分析两种催化机理(Langmuir-Hinshelwood和Eley-Rideal)对CO氧化反应的影响.与其它金属原子相比,Al原子掺杂的石墨烯体系具有极低的反应势垒(0.4 e V),更有助于CO氧化反应的迅速进行.     

Comparisons between adsorption and diffusion of alkali,alkaline earth metal atoms on silicene and those on silicane:Insight from first-principles calculations

The adsorption and diffusion behaviors of alkali and alkaline-earth metal atoms on silicane and silicene are both investigated by using a first-principles method within the frame of density functional theory.Silicane is staler against the metal adatoms than silicene.Hydrogenation makes the adsorption energies of various metal atoms considered in our calculations on silicane significantly lower than those on silicene.Similar diffusion energy barriers of alkali metal atoms on silicane and silicene could be observed.However,the diffusion energy barriers of alkali-earth metal atoms on silicane are essentially lower than those on silicene due to the small structural distortion and weak interaction between metal atoms and silicane substrate.Combining the adsorption energy with the diffusion energy barriers,it is found that the clustering would occur when depositing metal atoms on perfect hydrogenated silicene with relative high coverage.In order to avoid forming a metal cluster,we need to remove the hydrogen atoms from the silicane substrate to achieve the defective silicane.Our results are helpful for understanding the interaction between metal atoms and silicene-based two-dimensional materials.     

金属原子修饰石墨烯体系催化性能的理论研究

采用基于密度泛函理论的第一性原理方法研究了单个CO 和O2气体分子在金属原子修饰石墨烯表面的吸附和反应过程. 结果表明: 空位缺陷结构的石墨烯能够提高金属原子的稳定性, 金属原子掺杂的石墨烯体系能够调控气体分子的吸附特性. 通入混合的CO和O2作为反应气体, 石墨烯表面容易被吸附性更强的O2分子占据, 进而防止催化剂的CO 中毒. 此外, 对比分析两种催化机理(Langmuir-Hinshelwood和Eley-Rideal)对CO氧化反应的影响. 与其它金属原子相比, Al原子掺杂的石墨烯体系具有极低的反应势垒(< 0.4 eV), 更有助于CO氧化反应的迅速进行.     

A theoretical study of hydrogen adsorption and diffusion on a W(1 1 0) surface

We have used density functional theory to investigate hydrogen adsorption and diffusion on a W(1 1 0) surface. Hydrogen adsorption structures were examined from low coverage to one monolayer, and a threefold hollow site was found to be the most stable site at all coverages. In contrast to previous assertions, the work function decrease is not due to electron transfer from the hydrogen atoms to the W surface, but due to electron depletion at the vacuum region above the hydrogen atoms. Hydrogen atoms can diffuse via short-bridge sites and long-bridge sites at a coverage of θ = 1.0. Although the calculated activation energy for hydrogen diffusion via a short-bridge site is as small as 0.05 eV, field emission microscope experiments have shown that the activation energy for hydrogen diffusion is about 0.20 eV, which agrees fairly well with our calculated value of the activation energy via a long-bridge site. This discrepancy can be related to hydrogen delocalization on the W(1 1 0) surface, which has been suggested by electron energy loss spectroscopy experiments.     

锂薄膜的第一性原理计算:量子尺寸效应和原子氢的吸附

采用第一性原理方法计算Li（110）、（100）和（111）三个表面方向3至30层自由薄膜的表面能和氢原子的吸附能.随着层厚变化出现量子振荡现象,即量子尺寸效应.重点计算Li（110）表面吸附氢原子吸附高度、吸附氢原子前后费米能级处的态密度和功函数.这些量都随着层厚变化出现明显的量子振荡,且与表面能或吸附能的振荡有明显的相关性.计算发现Li（110）薄膜表面的功函数由于吸附氢原子而降低了约0.9 eV,吸附的氢原子拉低了最外层Li原子和真空层的静电势,导致吸附氢原子后功函数下降.     

Electron spin torque in atoms

The spin torque and zeta force, which govern spin dynamics, are studied by using monoatoms in their steady states. We find nonzero local spin torque in transition metal atoms, which is in balance with the counter torque, the zeta force. We show that d-orbital electrons have a crucial effect on these torques. Nonzero local chirality density in transition metal atoms is also found, though the electron mass has the effect to wash out nonzero chirality density. Distribution patterns of the chirality density are the same for Sc–Ni atoms, though the electron density distributions are different.     

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.     

Cs/GaN(0001)吸附体系电子结构和光学性质研究

采用基于第一性原理的密度泛函理论平面波超软赝势方法计算了 1/4ML Cs原子吸附 (2 × 2) GaN(0001) 表面的吸附能、能带结构、电子态密度、电荷布居数、功函数和光学性质. 计算发现, 1/4ML Cs 原子在 GaN(0001) 表面最稳定吸附位为 N 桥位, 吸附后表面仍呈现为金属导电特性, Cs原子吸附GaN(0001)表面后主要与表面 Ga 原子发生作用, Cs6s 态电子向最表面 Ga 原子转移, 引起表面功函数下降. 研究光学性质发现, Cs 原子吸附 GaN(0001) 表面后, 介电函数虚部、吸收谱、反射谱向低能方向移动.     

Theoretical study of interaction between atoms of Au, Ag, Cu and clean Si(1 1 1) surface

To evaluate the interactions between the atoms of Au, Ag and Cu and clean Si(1 1 1) surface, two types of silicon clusters Si₄H₇ and Si₁₆H₂₀ together with their metal complexes were studied by using hybrid (U)B3LYP density functional theory method. Optimized geometries and energies on different adsorption sites indicate that: (1) the binding energies at different adsorption sites are large (ranging from 1.2 to 2.6 eV depend on the metal atoms and adsorption sites), suggesting a strong interaction between metal atom and silicon surface; (2) the most favorable adsorption site is the on top (T) site. Mulliken population analysis indicated that in the system of on top (T) site, a covalent bond is formed between metal atom and dangling bond of surface Si atom.     

Specific features of the formation of ytterbium films on the Si(111) surface at room temperature

The processes accompanying the formation of ytterbium films on the Si(111) surface at room temperature are investigated by the contact potential difference method, Auger electron spectroscopy, low-energy electron diffraction, and thermal desorption spectroscopy. It is shown that the grown metal films are uniform in thickness and that Si atoms virtually do not dissolve in the films. The atoms of the silicon substrate can diffuse in limited amounts into the Yb metal film only when the surface is bombarded by high-energy primary electron beams employed in Auger electron spectroscopy. The results obtained permit the conclusion that the previously observed oscillations of the work function in Yb-Si(111) thin-film structures cannot originate from dissolution of silicon atoms in the ytterbium film.     

Density-functional study of Mo4S6 on Au(111)

The adsorption site and energetics of Mo₄S₆ on the unreconstructed (111) gold surface was determined by density-functional band-structure calculations. Mo₄S₆ adsorbs preferably via three S atoms at Au–Au bridging sites and three Mo atoms at adjacent threefold hollow sites of the Au(111) surface. The perfectly tetrahedral free cluster becomes trigonally distorted upon adsorption, which indicates the presence of attractive Au–S and Au–Mo interactions. The work of separation amounts to 4.2 eV including gradient corrections. Small peak shifts in the density of electronic states indicate electron transfer from Au to S states and from Mo to Au states, such that a Bader analysis yields a neutral cluster. Electron density difference maps, which visualize the electron redistribution between cluster and substrate in the interface region, show that the electron redistribution is confined to the cluster-surface contact region. PACS 61.46.+w; 73.22.-f; 72.20.-v     

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