A periodic density functional theory study of the dehydrogenation of methanol over CuCl(1 1 1) surface

The decomposition of methanol on clean and oxygen-precovered CuCl(1 1 1) surface have been studied with the method of density functional theory-generalized gradient approximation (DFT-GGA) and the periodic slab models. The effects of different methanol coverages up to one monolayer are investigated. The activation of the O-H bond of methanol to form the methoxide intermediate, the activation of the C-H bond to form the hydroxymethyl intermediate and the activation of the C-O bond to form methyl are examined. These intermediates can subsequently react to form methoxide, hydroxymethyl, methyl, formaldehyde, formyl, and finally CO on the surface. The chemisorption energies of CH₃OH, CH₃O, H₂COH, CH₃, H₂CO, HCO, OH and CO at their most favorable adsorption sites are predicted to be −57.9, −235.3, −172.9, −170.5, −67.8, −192.4, −309.5 and −105.7 kJ/mol, respectively. We also confirm that the O-H bond-breaking paths have lower energy barrier, compared to the C-O and C-H bond-breaking paths. However, these reactions need a lower energy barrier when precovered oxygen atoms participate in these reactions.     

Point-defect properties of,and sputtering events in,the {001} surfaces of Ni3Al. II. Sputtering events at and near surfaces

Atomic recoil events at and near {001} surfaces of Ni₃Al due to elastic collisions between electrons and atoms have been simulated by molecular dynamics to obtain the sputtering threshold energy as a function of atomic species, recoil direction and atomic layer of the primary recoil atom. The minimum sputtering energy occurs for adatoms and is 3.5 and 4.5?eV for Al and Ni adatoms on the Ni–Al surface (denoted ‘M’), respectively, and 4.5?eV for both species on the pure Ni surface (denoted ‘N’). For atoms within the surface plane, the minimum sputtering energy is 6.0?eV for Al and Ni atoms in the M plane and for Ni atoms in the N surface. The sputtering threshold energy increases with increasing angle, θ, between the recoil direction and surface normal, and is almost independent of azimuthal angle, ?, if θ<60°; it varies strongly with ? when θ>60°, with a maximum at ??=?45° due to ?{110}? close-packed atomic chains in the surface. The sputtering threshold energy increases significantly for subsurface recoils, except for those that generate efficient energy transfer to a surface atom by a replacement collision sequence. The implications of the results for the prediction of the mass loss due to sputtering during microanalysis in a FEG STEM are discussed.     

Analysis of the outermost atomic layer of a surface by low-energy ion scattering

Noble gas ion scattering is used to study the surface of solid targets. It is shown that this technique can be used to obtain a mass spectrum of the first atomic layer of the surface. Since the outermost atoms will largely determine the chemical reactivity and physical properties of the surface, this is an important property for an analytic tool to have. In addition to reflected ions, high-energy recoil ions are sometimes observed.Both the reflected and the recoil ions provide information about the atomic structure of the surface. The various possibilities of ion scattering are demonstrated for bromine, oxygen, sodium and potassium adsorbed on a Si(111) surface, for halogens adsorbed on Ni(100) and for GaP (110), (111) ($\text{111}$) surfaces. The influence of thermal vibrations of surface atoms and of electronic excitation on the spectra is discussed.     

The oxidation of methanol on a silver (110) catalyst

The oxidation of methanol was studied on a Ag(110) single-crystal by temperature programmed reaction spectroscopy. The Ag(110) surface was preoxidized with oxygen-18, and deuterated methanol, CH₃OD, was used to distinguish the hydroxyl hydrogen from the methyl hydrogens. Very little methanol chemisorbed on the oxygen-free Ag(110) surface, and the ability of the silver surface to dissociatively chemisorb methanol was greatly enhanced by surface oxygen. CH₃OD was selectively oxidized upon adsorption at 180 K to adsorbed CH₃O and D₂¹⁸O, and at high coverages the D₂¹⁸O was displaced from the Ag(110) surface. The methoxide species was the most abundant surface intermediate and decomposed via reaction channels at 250, 300 and 340 K to H₂CO and hydrogen. Adsorbed H₂CO also reacted with adsorbed CH₃O to form H₂COOCH₃which subsequently yielded HCOOCH₃ and hydrogen. The first-order rate constant for the dehydrogenation of D₂COOCH₃ to DCOOCH₃ and deuterium was found to be (2.4 ± 2.0) × 10¹¹ exp(?14.0 ± 0.5 $\text{kcal}\text{mole}$ · RT)sec^?1. This reaction is analogous to alkoxide transfer from metal alkoxides to aldehydes in the liquid phase. Excess surface oxygen atoms on the silver substrate resulted in the further oxidation of adsorbed H₂CO to carbon dioxide and water. The oxidation of methanol on Ag(110) is compared to the previous study on Cu(110).     

A semiempirical formula describing the recoil yield in silicon

Krypton ions in the energy range 20–300 keV are used to generate recoiling atoms in silicon from thin layers evaporated on its surface. The recoil yields and the impurity distributions in the substrate have been measured as a function of several parameters (energy, thickness of the layer, incident dose). The results are used to propose a new formulation of the recoil yield based on the possibility, for both projectiles and recoiling atoms, to remove impurities previously introduced in silicon.The calculation fits very well the experimental results using displacement energies close to the generally admitted values     

Ion bombardment induced decomposition of polyimide (PIQ) studied by X-ray Photoelectron Spectroscopy (XPS) and Direct Recoil (DR) spectrometry

Angular resolved X-ray photoelectron spectroscopy (XPS) and time-of-flight direct recoil (DR) spectrometry are used to characterize the surface changes in polyimide iso-indroquinazolinedione (PIQ®: Hitachi Chem. Co.) induced by 4 keV Ar⁺ bombardment. Deconvolution of the XPS data along with a stoichiometry of CH_{2.2 ± 0.2} as determined from DR intensities indicate the presence of an uppermost hydrocarbon layer on the initial surface. Upon Ar⁺ bombardment the H, N, and O concentrations decrease and the surface layer carbon concentration increases to > 94 at %. This carbonaceous layer exhibits C1s chemical shifts and line shapes that are similar to those of an ion bombarded graphite surface, along with an enhanced electrical conductivity.     

The use of direct recoil spectrometry (DRS) for the study of water vapor interactions on polycrystalline metallic surfaces—the H2O/U and H2O/Ti systems

Using direct recoil spectrometry (DRS), the shadowing of surface H atoms by neighboring O atoms can differentiate between full and partial dissociation routes of water molecules on the surface as well as point to the geometrical arrangements of hydroxyl surface groups. The H₂O/U and H₂O/Ti systems were compared. It has been found that different mechanisms control the water-surface interactions in these systems.For the H₂O/U system, a simple direct-collision (Langmuir-type) dissociative chemisorption controls the process. Two consecutive stages were identified: (i) below ∼70% monolayer coverage, a complete dissociation of water into oxygen ion and two H atoms, which chemisorb on the remaining unreacted metallic surface and (ii) above about 70% of a full layer coverage, three dimensional oxide islands start to form, causing partial dissociation of water and the formation of surface hydroxyls.For the H₂O/Ti system, a more complicated mechanism, which involves a precursor state, seems to control the process. In that case, two concurrent routes act simultaneously. In addition to the simple direct-collision mechanism, water precursor clusters (bound by hydrogen bonds), which partly dissociate, result in chemisorbed tilted hydroxyl clusters (even at low-coverage). The relative contributions of the precursor route and the direct-collision route are pressure dependent, with the former being dominant at higher exposure pressures.     

Interactions of water vapor with polycrystalline uranium surfaces

The initial room-temperature interactions of water vapor with polycrystalline bulk annealed uranium surfaces were studied by combined measurements utilizing direct recoil spectrometry (DRS) and X-ray photoelectron spectroscopy (XPS). It was found that the water goes through a complete dissociation into oxidic oxygen and two neutral H atoms throughout the whole exposure range. The process proceeds by two consecutive stages: (i) below about 80% monolayer coverage, the dissociation products chemisorb mainly on the remaining non-reacted metallic surface by a simple Langmuir-type process; (ii) between about 80% and full coverage, three-dimensional oxide islands (that start to form at 50-60% coverage) cover most of the surface and full dissociation continues on top of them. It seems that on top of the oxide the dissociation consists of a two-step process: first partial dissociation into OH⁻ + H⁰, where the neutral hydrogen atom chemisorbs on the oxide and the hydroxyl group migrates into the subsurface region and then undergoes a reductive dissociation at the oxide-metal interface, producing a second hydrogen atom, located beneath the surface.     

Localized vacancies in palladium produced by thermal neutron capture recoil

The environment of recoil atoms in Pd metal after the (n, γ)-process in ¹¹⁰Pd at low temperatures has been studied by perturbed angular correlations of ¹¹¹Cd probes. It shows that 19(1) % of the recoil atoms have a vacancy as nearest neighbour.     

Range of recoil atoms in isotropic stopping materials

A calculation of the stopping power, range, and range straggling of low energetic atoms (E?1 MeV) is reported. The computation applied the biatomic repulsive potential of Firsov and thus had to be carried out numerically. The results, however, are presented in an analytical form. — Experimental checks were performed with recoil atoms. 96 keV Ra-224 atoms from the α-decay of Th-228 were used to measure the range distributions in several light gases. — The fast neutron induced reactions, such as (n, p)-or (n, α)-reactions, led to recoils of higher energies (up to more than 1 MeV). Their mean ranges in polycrystalline metals or amorphous oxide layers could be obtained by measuring the fraction of radioactive recoils which had left the target surface. — The experimental data are in good agreement with the theory, except at the highest energies where the observed ranges are slightly larger than predicted.     

Elastic Energy Losses and Orientation Effects during Interaction between Atomic Particles

Patterns of energy transfer and accumulation in elastic interactions between Nb⁺ ions (E₀ = 0.1–3 keV) and atoms of a Nb single crystal are studied by means of molecular dynamics. Spatial distributions of the recoil energy in the bulk of the crystal are calculated. It is shown that recoil energy is accumulated in the region of the densest packing of atoms, mainly in the outermost (N = 1–3) monolayers of the crystal. The effect the orientation of the target with respect to the beam has on the recoil energy and its spatial distributions is determined.     

Low-energy sputtering events at free surfaces near anti-phase and grain boundaries in Ni3Al

Atomic recoil events on free surfaces orthogonal to two different anti-phase boundaries (APBs) and two grain boundaries (GBs) in Ni₃Al are simulated using molecular dynamics methods. The threshold energy for sputtering, E _sp, and adatom creation, E _ad, are determined as a function of recoil direction. The study is relevant to FEG STEM (a scanning transmission electron microscope fitted with a field emission gun) experiments on preferential Al sputtering and/or enhancement of the Ni–Al ratio near boundaries. Surfaces intersected by {110} and {111} APBs have minimum E _sp of 6.5?eV for an Al atom on the Ni–Al mixed (M) surface, which is close to the value of 6.0?eV for a perfect M surface. High values of E _sp of an Al atom generally occur at a large angle to the surface normal and depend strongly on the detailed atomic configuration of the surface. The mean E _sp, averaged over all recoil directions, reveals that APBs have a small effect on the threshold sputtering. However, the results for E _ad imply that an electron beam could create more Al adatoms on surfaces intersected by APBs than on those without. The equilibrium, minimum energy structures for a (001) surface intersected by either Σ5[001](210) or Σ25[001](340) symmetric tilt grain boundaries are computed. E _sp for surface Al atoms near these GBs increases monotonically with increasing recoil angle to the surface normal, with a minimum value, which is only about 1?eV different from that obtained for a perfect surface. Temperature up to 300?K has no effect on this result. It is concluded that the experimental observations of preferential sputtering are due to effects beyond those for E _sp studied here. Possible reasons for this are discussed.     

Adsorption of methanol,formaldehyde and formic acid on Pd(100) surfaces modified by a sodium and sodium oxide overlayer

The effect of a sodium and sodium oxide overlayer on a Pd(100) surface has been investigated by AES, LEED, XPS, UPS and TPRS methods. Ordered surface structures of (4 × 4), (2 × 2) and c(2 × 2) were observed for a sodium overlayer, which was contracted by the adsorption of oxygen. The increase of bonding energy of CO, H₂ as well as CO₂ was confirmed on both sodium and sodium oxide covered surfaces, and three adsorption states were distinguished for CO₂ on these surfaces. For the adsorption of methanol, formaldehyde and formic acid, the interaction was also strengthened on the sodium covered surface. As a result, the concentration as well as the stability of surface methoxide and formate was significantly increased and the strong interaction between formaldehyde and surface oxygen was confirmed.     

XPS,UPS and thermal desorption studies of alcohol adsorption on Cu(110): II. Higher alcohols

Preceding work dealing with the adsorption of methanol on Cu(110) has been extended to include ethanol, n- and iso-propanol and a diol, ethylene glycol. In common with the simplest alcohol, all these molecules are able to form a stable alkoxy species on the surface, that is, the alcohol dissociated at the O-H group. However, in contrast to methanol on the clean surface for which the dissociated methoxy and hydrogen recombined to desorb as methanol, all the higher alcohols reacted further with the surface, dehydrogenating to yield the corresponding aldehyde or ketone in the gas phase. Ethylene glycol reacted to form the most strongly bound intermediate of all, decomposing near 390 K to produce the dialdehyde, glyoxal, with little evidence of monoaldehyde formation or C-C bond breakage. The influence of pre-adsorbed oxygen on these reactions was to generally increase the amount of alkoxy formed on the surface by enhancing the amount of dissociative adsorption (water is formed by the deprotonation of adsorbed alcohol molecules by oxygen atoms). The alkoxide decomposition peaks were shifted to slightly higher temperatures and considerably broadened in such experiments. The decomposition peak temperatures of the different surface alkoxides correlate fairly well with literature values of the αC-H bond strength, which is weaker in iso-propanol than in methanol. XPS showed broad O(1s) spectra for all the molecules adsorbed at 140 K, probably due to hydrogen-bonding effects in the adlayer, with peak emissions at around 533 eV. When the surface was warmed to 250 K, the O(1s) spectra narrowed to close to instrumental linewidths with a concomitant shift to a lower binding energy near 531 eV. C(1s) spectra showed little change between the adsorbed alcohol and alkoxy species. The UPS showed low temperature spectra similar to the gas phase, but the highest occupied orbitals, which are essentially O(2p) orbitals, showed a chemisorption bonding shift of several tenths of an electron volt. UPS for these molecules is shown to have considerable less utility than for the simplest molecule, methanol, due to the masking of possible orbital shifts during chemical changes on the surface by the presence of overlapping emissions in the spectra.     

低能原子簇轰击金属薄膜引起的级联碰撞(Ⅰ)——高能反冲原子

用分子动力学模拟研究能量为1keV/atom的Au原子簇和0.2keV/atom的Al原子簇轰击金薄膜产生的级联碰撞。分子动力学模拟结果表明,原子簇轰击后,靶原子的反冲能谱加宽。与同样速度的单原子轰击比较,最大反冲能较后者高2—5倍。原子簇轰击后的多次碰撞及运动原子间的碰撞增加了靶原子的反冲能。还用经典力学守恒定律分析了两个碰撞的运动原子间的能量转移。 关键词：     

Surface physics with radioactive ion beams

Nuclear methods using radiation detection are very well suited for surface and interface investigations, since they generally require only a small number of radioactive probe nuclei. Virtually isolated probe atoms can be investigated. The use of an isotope separator to solve the central problem in the application of radioactive atoms for the study of surfaces, the clean deposition of the probe nuclei, is described. First physics experiments include studies of desorption isochrones and characterization of adatom sites on flat and vicinal surfaces by PAC. A particularly complete picture could be obtained for Cd and In on the Pd(111) surface, where five different sites successively populated in the surface diffusion process were observed. Other nuclear methods suitable for a future extension of the surface investigations, such as Mössbauer spectroscopy, decay recoil angular distribution and emission channeling, are briefly discussed.     

甲醇在Pt (100)表面吸附与解离的第一性原理研究.

采用基于第一性原理的密度泛函理论结合周期模型方法对甲醇在Pt(100)完整表面的吸附与解离进行了研究. 通过比较不同吸附位置的吸附能与构型参数发现,表面top吸附位为最稳定吸附位,甲醇分子通过氧原子吸附于Pt(100)表面. 同时计算了甲醇分子在top吸附位可能的解离路径,发现在解离过程中OH键首先断裂的路径为最低能量路径. 分解生成的若干产物其吸附稳定性排序为CH₃O>CH₂OH>CH₃>CH₂O.     

Determination of the coverage of ethylene and ethylidyne on Pt(111) using elastic recoil detection analysis

Very high energy ions incident upon a sample with adsorbed light adatoms will cause some of the adsorbates to recoil off the surface with substantial amounts of energy. The number of recoil particles is a direct measure of the adatom concentration. Using this technique (elastic recoil detection analysis or ERDA), we have determined the concentration of adsorbed ethylene (C₂H₄) and ethylidyne (C₂H₃) on Pt(111). We find, both for adsorption below and at room temperature, that the coverage is approximately one half of a monolayer, in agreement with earlier work using X-ray photoelectron spectroscopy. We propose that the adsorbed ethylidyne molecules form a honeycomb lattice.     

Can sub-GeV dark matter coherently scatter on the electrons in the atom?

A novel detection of sub-GeV dark matter is proposed in the paper.The electron cloud is boosted by the dark matter and emits an electron when it is dragged back by the heavy nucleus,namely the coherent scattering of the electron cloud of the atom.The survey in the x-ray diffraction shows that the atomic form factors are much more complex than the naive consideration.The results of the relativistic Hartree-Fock(RHF) method give non-trivial shapes of the atoms.The detailed calculation of the recoi...     

Computer simulation of fast recoil ejection from single crystal surfaces

The computer simulation program MARLOWE is used to analyze the most probable surface recoil processes leading to ejection of atoms from (001) gold surfaces subsequent to the irradiation with 20 keV argon atoms. The occurence of two-and threedimensional mechanisms resulting from high-energy recoils involving one and two atomic layers is discussed for atoms ejected in a direction parallel to the plane of incidence. Generally, a close correspondence is found between the mechanisms involved and the features in the energy distributions. The occurence of direct and deflected recoils is confirmed, as well as mechanisms involving the generation of displacements in the two first atomic layers. The dependence of these mechanisms on the conditions of incidence and the ejection direction is investigated. It is suggested that three-dimensional effects, although dominating, mainly contribute to the background in the energy distributions. The intensities in the features in the energy distributions were found to be strongly influenced by shadowing; affecting both the one-and two-layer processes. The influence of thermal vibrations, surface defects and impurities is briefly examined.