Role of molecular orbitals near the fermi level in the excitation of vibrational modes of a single molecule at a scanning tunneling microscope junction

Inelastically tunneled electrons from the tip of a scanning tunneling microscope were used to induce S-S bond dissociation of a (CH(3)S)(2) and lateral hopping of a CH(3)S on Cu(111) at 4.7 K. Both experimental results and theoretical calculations confirm that the excitation mechanism of the vibrationally induced chemistry reflects the projected density of states of molecular orbitals that appear near the Fermi level as a result of the rehybridization of the orbitals between the adsorbed molecules and the substrate metal atoms.     

Metal work-function changes induced by organic adsorbates: a combined experimental and theoretical study

The role of molecular dipole moment, charge transfer, and Pauli repulsion in determining the work-function change (Deltaphi) at organic-metal interfaces has been elucidated by a combined experimental and theoretical study of (CH(3)S)(2)/Au(111) and CH(3)S/Au(111). Comparison between experiment and theory allows us to determine the origin of the interface dipole layer for both phases. For CH(3)S/Au(111), Deltaphi can be ascribed almost entirely to the dipole moment of the CH(3)S layer. For (CH(3)S)(2)/Au(111), a Pauli repulsion mechanism occurs. The implications of these results on the interpretation of Deltaphi in the presence of strongly and weakly adsorbed molecules is discussed.     

Following local adsorption sites through a surface chemical reaction: CH3SH on Cu(111)

Studying the interaction of CH3SH, methanethiol, with Cu(111) as a model system, we demonstrate the ability of chemical-shift normal incidence x-ray standing wave field measurements to identify the local adsorption geometries of coadsorbed reaction products at different temperatures, a technical problem of broad chemical significance. In the present case the local geometries of four distinct S-containing adsorbate species (intact CH3SH, two thiolate (CH3S-) reaction intermediates and atomic S) are determined.     

Adsorption Behavior of CH2 and CH3 on Metal Clusters Cun (n=1-6)

利用密度泛函理论(DFT)中的广义梯度近似(PW91)和杂化泛函(B3LYP)两种理论方法,计算了小分子CH2和CH3在Cun(n=1～6)团簇上的吸附能、电荷布局和振动等吸附性质. 结果表明,B3LYP方法得到的CH2和CH3吸附在Cun团簇上的结果更好一些;CH2在Cun团簇上的吸附要比CH3的吸附强. 吸附过程中也发生电荷从金属Cun团簇上转移到CH2和CH3上的现象. 计算得到的C-H键的振动频率与实验上测量的这两个分子吸附在Cu(111)表面的结果符合得很好     

Cu~+、Ag~+、Au~+与乙硫醇的气相化学反应

利用激光溅射 分子束的技术 ,结合反射飞行时间质谱计 ,研究了Cu+、Ag+、Au+与乙硫醇的气相化学反应。结果显示这三种金属离子与 (CH3 CH2 SH) n 反应形成一系列团簇离子M+(CH3 CH2 SH) n,且团簇离子尺寸不一样。Ag+、Au+与乙硫醇的反应还生成了 (CH3 CH2 SH) +n ,由此推测Cu+、Ag+、Au+与乙硫醇团簇的反应存在两种通道 ,一种通道是生成M+(CH3 CH2 SH) n,另一种是生成 (CH3 CH2 SH) +n 。Cu+、Au+与乙硫醇的反应还生成了M+(H2 S) (M =Cu、Au) ,但是实验中没有观察到Ag+(H2 S) ,理论计算表明Ag+(H2 S)很不稳定。另外 ,分析产物离子M+(CH3 CH2 SH) n 的强度发现 ,n =1～ 2之间存在明显的强度突变现象     

Formation and diffusion of S-decorated Cu clusters on Cu(111)

S-decorated Cu trimers are a likely agent of S-enhanced Cu transport between islands on Cu(111). According to ab initio calculations, excellent S bonding to trimer-Cu dangling valence results in an ad- Cu(3)S(3) formation energy of only approximately 0.28 eV, compared to 0.79 eV for a self-adsorbed Cu atom, and a diffusion barrier < or =0. 35 eV.     

NEXAFS study of 1-butanethiol adsorbed on Cu(111) and square root of 7 x square root of 7 R19.1 degrees S/Cu(111)

The adsorption of 1-butanethiol on Cu(111) and square root of 7 x square root of 7 R19.1 degrees S/Cu(111) surfaces has been studied by S K-edge near edge X-ray absorption fine structure (NEXAFS) spectroscopy and thermal desorption spectroscopy. Upon adsorption on clean Cu(111) surface at room temperature, butanethiolate as well as atomic sulfur is formed. For the butanethiolate, the S-C bond is found predominately perpendicular to the surface as revealed by polarization analysis. In contrast, on square root of 7 x square root of 7 R19.1 degrees S/Cu(111) surface, the S-H and S-C bonds of the butanethiol stay intact, resulting in a weakly chemisorbed butanethiol.     

Enhanced self-diffusion on Cu(111) by trace amounts of s: chemical-reaction-limited kinetics

We find that less than 0.01 monolayer of S can enhance surface self-diffusion on Cu(111) by several orders of magnitude. The measured dependence of two-dimensional island decay rates on S coverage (theta(S)) is consistent with the proposal that Cu3S3 clusters are responsible for the enhancement. Unexpectedly, the decay and ripening are diffusion limited with very low and very high theta(S) but not for intermediate theta(S). To explain this result we propose that surface mass transport in the intermediate region is limited by the rate of reaction to form Cu3S3 clusters on the terraces.     

甲基和羟基在Ir(111)表面吸附的密度泛函理论研究

在超原胞近似和slab模型基础上,采用周期性密度泛函理论,在0.11覆盖度（ML）下,对甲基与羟基在Ir(111)表面的吸附进行了研究,得到了甲基和羟基在Ir(111)表面不同吸附位置的吸附能和吸附构型,计算了它们的振动频率,同时分析了甲基和羟基共吸附于Ir(111)表面的情况。结果表明,甲基和羟基在Ir(111)表面的最稳定吸附位置都是top位,甲基是碳端向下吸附,羟基是通过氧端向下倾斜吸附。通过频率分析发现吸附后CH3中C-H键的对称伸缩振动、反对称伸缩振动以及剪切振动频率均发生了红移,而羟基中的O-H键的振动频率发生蓝移现象。通过计算对比发现甲醇分解为甲基和羟基过程是一个放热反应,从热力学角度来说该反应是可行的。     

Do methanethiol adsorbates on the Au(111) surface dissociate?

The interaction of methanethiol molecules CH3SH with the Au(111) surface is investigated, and it is found for the first time that the S-H bond remains intact when the methanethiol molecules are adsorbed on the regular Au(111) surface. However, it breaks if defects are present in the Au(111) surface. At low coverage, the fcc region is favored for S atom adsorption, but at saturated coverage the adsorption energies at various sites are almost isoenergetic. The presented calculations show that a methanethiol layer on the regular Au(111) surface does not dimerize.     

Adsorption of thiolates to singly coordinated sites on Au111 evidenced by photoelectron diffraction

The adsorption structure of methylthiolate (CH3S) adsorbed on Au(111), a long-standing controversial issue, has been unambiguously determined by scanned-energy and scanned-angle S 2p photoelectron diffraction. The methylthiolate molecules are found to occupy atop sites with a S-Au distance of 2.42 +/- 0.03 A. The angular distribution of the S 2p photoelectrons due to forward scattering reveals that the S-C bond is inclined by approximately 50 degrees from the surface normal towards both the [211] and [121] (nearest-neighbor thiolate) directions.     

Study of chemisorption on copper low-index and stepped surfaces

Adsorption of CHCl₃, O₂, and hydrocarbons has been studied on Cu(111) and stepped surfaces using LEED, AES, and UPS at room temperature. We find that ordered Cl overlayers form upon Cu(111), Cu[3(111) × (100)], and Cu[5(111) × (100)] surfaces upon exposure to CHCl₃. Exposure to O₂ results in rearrangement of the Cu[5(111) × (100)] surface to hill-and-valley regions with large (111) areas, whereas Cu[2(111) × (100)] is stable for the same exposure. The photoemission spectra show new energy levels due to C1 above and below the Cu d band region and a small splitting of the halogen p orbitals. Effects consistent with interaction with the Cu d band are observed. Similar effects are observed with oxygen adsorption. The initial rate of Cl or O₂ chemisorption as measured by photoemission is proportional to the density of steps on these surfaces. Apparently, structural effects play an important role in chemisorption on metals (such as copper) with low density of states at the Fermi energy.     

Adsorption-desorption properties and surface structural chemistry of chlorine on Cu(111) and Ag(111)

The adsorption, desorption, and structural properties of chlorine adlayers on Cu(111) and Ag(111) have been studied by LEED, Auger, Δ?, and thermal desorption measurements. Ancillary experiments were also carried out on cuprous chloride for purposes of comparison with the Cu(111)-Cl data. Chlorine adsorption is rapid on both metals and follows precursor kinetics, the absolute initial sticking probabilities being ~1.0 (Cu) and ~0.5 (Ag). Δ? results suggest that significant depolarisation of the chemisorption bond occurs at high coverages, the maximum values being + 1.2 eV (Cu) and + 1.8 eV (Ag). On Cu(111), adsorption leads to the formation of a sequence of well-ordered phases; in order of increasing coverage, these are as follows: (√3 × √3)R30°, (12√3 × 12√3)R30°, (4√7 × 4√7)R19.2°, and (6√3 × 6√3)R30°. On Ag(111) (√3 × √3)R30°, and (10 × 10) structures are observed. All six structures are susceptible to a straightforward interpretation in terms of coincidence lattices resulting from the progressive uniform compression of a hexagonal layer of Cl atoms. This interpretation is consistent with all the experimental results, and gives values for the nearest-neighbour ClCl spacing on both Cu(111) and Ag(111) which are in good agreement with other work on other surfaces. Chlorine desorbs exclusively as atoms from both metals with first-order desorption kinetics, and apparent desorption energies of 236 (Cu) and 209 (Ag) kJ mol^?1. These values, which depend on an assumed pre-exponential factor of 10¹³ s^?1, are shown to be inconsistent with the thermochemical constraints on the system necessitated by the complete absence of Cl₂ desorption. Lower limits for the pre-exponential factors are then deduced, and the values are found to be consistent with the differences between the CuCl and AgCl systems.     

Nuclear magnetic resonance study of epitaxial Co layers on single-crystal substrates

Nuclear magnetic resonance (NMR) is a powerful tool to study the local structure of ultrathin magnetic films and multilayers. This is demonstrated with an NMR study of ultrathin molecular beam epitaxy-grown Co layers on single-crystal Cu(111), Cu(110) and Pd(111) substrates. Co on Cu(111) results in a mixture of fcc and hep phases and the Cu(111)/Co interface is near to perfect. Co on Cu(110) grows mainly fcc in long stripe-shaped islands with rough Co/Cu interfaces. Finally, Co on Pd(111) gives a (111)-oriented fcc structure. The top surface is flat, but the Pd(111)/Co surface is intermixed.     

First-principles calculation of ZnS monolayer on Cu(111) surface

First-principles calculation is carried out on the interface of the ZnS(001) monolayerand Cu(111) surface. It is found that the ZnS monolayer significantly reconstructs aftergeometry optimization. The out-of-plane S atom has a positive displacement in thez directionwhile other atoms (Zn and S) have small displacements on the ZnS monolayer. The interfacestacking sequence has an influence on the flatness of the ZnS monolayer and the bindingenergy of the interface. There are two approaches for the ZnS monolayer to reach thelowest energy state which take place on the two kinds of S atoms in the ZnS monolayer andresult in the bulging feature. The van der Waals (vdW) interaction exists between ZnSmonolayer and Cu surface.     

NO dissociation on Cu(111) and Cu2O(111) surfaces: a density functional theory based study

NO dissociation on Cu(111) and Cu(2)O(111) surfaces is investigated using spin-polarized density functional theory. This is to verify the possibility of using Cu-based catalyst for NO dissociation which is the rate limiting step for the NO(x) reduction process. The dissociation of molecularly adsorbed NO on the surface is activated for both cases. However, from the reaction path of the NO-Cu(2)O(111) system, the calculated transition state lies below the reference energy which indicates the possibility of dissociation. For the NO-Cu(111) system, the reaction path shows that NO desorption is more likely to occur. The geometric and electronic structure of the Cu(2)O(111) surface indicates that the surface Cu atoms stabilize themselves with reference to the O atom in the subsurface. The interaction results in modification of the electronic structure of the surface Cu atoms of Cu(2)O(111) which greatly affects the adsorption and dissociation of NO. This phenomenon further explains the obtained differences in the dissociation pathways of NO on the surfaces.     

The interaction of acetylene with Ni(111), chemisorbed oxygen on Ni(111), and NiO(111); the formation of CH species on chemically modified Ni(111) surfaces

Ultraviolet photoelectron spectroscopy, temperature programmed thermal desorption and low-energy electron diffraction have been used to study the interaction of acetylene with a clean Ni(111) surface, with a Ni(111) surface having co-adsorbed oxygen and with an epitaxially grown NiO(111) surface produced by room temperature oxidation ofNi(111). The adsorption of a (2 × 2) overiayer of π-bonded acetylene or oxygen on the Ni(111) surface markedly alters the subsequent interaction and reaction of the surface with incident acetylene. We find that in the presence of either a (2 × 2) overiayer of oxygen or π-bonded acetylene, a new more strongly bound hydrocarbon phase forms at room temperature. We identify this new phase from its ionization levels as a CH species, and for saturation coverages we find approximately twice as many of these species as the number of π-bonded acetylene molecules in the (2 × 2) structure. Preadsorption of oxygen limits the adsorption of π-bonded acetylene but does not affect the subsequent formation of this CH species. Exposure of acetylene to NiO at room temperature produces only CH species. Based upon these results we propose idealized models for the bonding geometry of π-bonded acetylene and CH species on the Ni(111) surface. The conditions for the formation of CH species and the significance of CH species to surface reactions on Ni are also discussed.     

Precursor film controlled wetting of Pb on Cu

Wetting in a system where the kinetics of drop spreading are controlled by the rate of formation of a precursor film is modeled for the first time at the atomistic scale. Molecular dynamics simulations of Pb(l) wetting Cu(111) and Cu(100) show that a precursor film of atomic thickness evolves and spreads diffusively. This precursor film spreads significantly faster on Cu(111) than on Cu(100). For Cu(100), the kinetics of drop spreading are dramatically decreased by slow advancement of the precursor film. Slow precursor film kinetics on Cu(100) are partly due to the formation of a surface alloy at the solid-liquid interface which does not occur on Cu(111).     

Low-temperature measurements of the fraction of re-emitted positronium from a Cu(111)+S surface

A positron beam has been utilized to measure the positronium (Ps) fraction re-emitted from a Cu(111)+S sample from 40 K to 350 K for incident energies ranging from 0.5 to 5 keV. Our results at 525 eV incident energy are compared with two recent theories from 40 K to 850 K. The Ps fraction shows only a slight positive temperature dependence below room temperature and we conclude that the positron trapping rate and probability of Ps formation at the surface are largely independent of sample temperature for Cu(111)+S. In addition we present evidence that positrons in the bulk material are not localized in shallow traps at low temperatures for well-annealed high-purity single crystals of Cu and Al.     

Local effect of Na adsorption on Cu(111)

The local effect of Na adsorbed on Cu(111) at very low coverage is studied with the Density Functional Theory. We find that the Na atom and its three nearest neighbor Cu atoms tend to form a small cluster, with the Na effect on surface being localized. The Mulliken occupation, density of state, interatomic energy, and interorbital energy show that the electron transfer mainly occurs from the 2p and 3s orbitals of Na atom to the 3d and 4s orbitals of the nearest neighbor Cu atoms, with the formation of a bond with four components that have different energies. In the anti-bonding state region, the 2p state of Na plays a key role in the bond, while in the bonding state region, not only the 2p state of Na has a very significant contribution, but the 3s state (which is the outermost Na orbital) also contributes to the bond between Na and the Cu(111) surface.