Co chemisorption on PtCu surfaces III. CO on PtCu(111)

Selected thermal desorption and valence band photoemission data on the chemisorption of CO on PtCu(111) surfaces are presented. The main objective is to make a comparison with CO chemisorption on an annealed (1 × 3) reconstructed Pt_0.98Cu_0.02(110) surface. The (111) alloy surfaces are unreconstructed (1 × 1) surfaces, with average near-surface Cu concentrations ranging from ? 7.5% to ? 20% as indicated by the Cu 920 eV Auger signal. It is observed that the effect of alloying Pt(111) with Cu is to progressively lower the desorption peak temperature and hence the free energy of CO desorption from Pt sites. A second observation is that the energy distribution of the Cu 3d-derived states is little affected by CO adsorption on Cu sites at 155 K. Both these results offer a contrast to the results for CO/Pt_0.98Cu_0.02(110) reported earlier.     

An ISS,AES, and CO chemisorption study of titania overlayers on Rh(111)

Ion scattering spectroscopy (ISS), Auger electron spectroscopy (AES) and crystal current measurements have been used to characterize the growth of titania overlayers deposited on a Rh(111) surface. Titania grows two-dimensionally during the first monolayer, with subsequent growth nearly layer-by-layer. The results show agreement among ISS, AES, and crystal current measurements in determination of monolayer coverage. The effect of titania on the chemisorption of CO on Rh(111) has also been investigated and compared with previous studies of titania deposited on Group VIII metals. Temperature-programmed desorption (TPD) of CO shows that titania has relatively little effect on the desorption energy of CO, and that the chemisorption capacity is proportional to the exposed Rh area. The results support a site-blocking model of chemisorption suppression.     

Nature of versatile chemisorption on TiC(111) and TiN(111) surfaces

Density-functional calculations on the polar TiX(111) (X = C, N) surfaces show (i) for clean surfaces, strong Ti3d-derived surface resonances (SR’s) at the Fermi level and X2p-derived SR’s deep in the upper valence band and (ii) for adatoms in periods 1-3, pyramidic trends in atomic adsorption energies, peaking at oxygen (9 eV). A concerted-coupling model, where adatom states couple to both kinds of SR’s in a concerted way, describes the adsorption. The chemisorption versatility and the general nature of the model indicate ramifications and predictive abilities in, e.g., growth and catalysis.     

Embedded cluster calculations for hydrogen chemisorption on the (111) surfaces of fcc Co,Ni, Cu,Rh, Pd and Ag

We present a muffin tin based calculation on (TM)₃H, (TM)₇H and (TM)₁₉H clusters embedded at the surface of an effective jellium-like medium whose potential is treated in scattering length approximation. We consider the changes occurring when the d-like perturbation of the TM muffin tins is switched on. The broad chemisorption-induced resonance seen for H on the effective jellium surface is narrowed and shifted down in energy. Furthermore the occupation of this resonance is increased from about 1.1 electrons to about 1.4 (on 3d metals) or 1.8 (on 4d metals), due to d-like states dropping down from the d band to form a relatively welldefined “bonding state”. An antibonding state containing about 0.4 electrons is formed at the top of the d band. The results are compared with other calculations and with photoemission data. Implications for the metal-hydrogen distance and (for Ni) the demagnetizing effect of hydrogen chemisorption are discussed. We use the change in total single particle energy when the d-like perturbation is switched on to estimate trends in chemisorption energy along the 3d and 4d series. In the 3d case experimental data is available on the difference in chemisorption energy between Ni and Cu which is in reasonable agreement with our estimate.     

The process of oxygen chemisorption on the Si(111) surface

The chemisorption of oxygen on the Si(111) surface has been studied by the ASED-MO method. Three steps of the initial oxidation process have been proposed. The first step is molecular oxygen chemisorption. The second step is that of dissociated oxygen chemisorption in which the atomic short bridge site (between the first layer and second layer silicon atoms) can be occupied only after the saturation of the dangling bonds of the surface silicon with oxygen. The third step is the diffusion of atomic oxygen from the short bridge positions into the bulk of silicon to form an SiO₂ film. For molecular chemisorption, both the peroxy vertical and peroxy bridge models are possible although the peroxy vertical model is the more stable. The dissociated atomic oxygen can chemisorb for both the on-top and the short bridge models. Our results can explain, and are consistent with, most experimental results.     

Pyridine chemisorption on silicon and germanium (111) surfaces

The chemisorption of pyridine molecules on cleaved Si(111) and Ge(111) surfaces was investigated by ultraviolet photoemission spectroscopy with synchrotron radiation. Evidence was found that the chemisorption process strongly affects all the three highest occupied molecular levels, i.e. the n-level and the two π-levels la₂ and 2b₂. This result was used to rule out a chemisorption geometry with the aromatic ring parallel to the surface. In the most likely chemisorption geometry the ring is tilted with respect to the substrate and the n-orbital plays a leading role in the formation of chemisorption bonds.     

Some coadsorption effects on Rh(111)

ESD energy analysis is used to study the reaction products produced during coadsorption of CO-O₂ and CH₄-O₂ on Rh(111). Residence of CO₂ on the surface is confirmed by detection of a CO₂⁺ ionic component with energy of 1.8 eV. Adsorption and dissociation of CH₄ on oxygen- covered Rh(111) is inferred as a result of a low energy component present in the energy spectra of desorbed O⁺.     

The co-adsorption of oxygen and hydrogen on Rh(111)

The co-adsorption of oxygen and hydrogen on Rh(111) at temperatures below 140 K has been studied by thermal desorption mass spectrometry, Auger electron spectroscopy, and lowenergy electron diffraction. The co-adsorption phenomena observed were dependent upon the sequence of adsorption in preparing the co-adsorbed overlayer. It has been found that oxygen extensively blocks sites for subsequent hydrogen adsorption and that the interaction splits the hydrogen thermal desorption into two states. The capacity of the oxygenated Rh(111) surface for hydrogen adsorption is very sensitive to the structure of the oxygen overlayer, with a disordered oxygen layer exhibiting the lowest capacity for hydrogen chemisorption. Studies with hydrogen pre-adsorption indicate that a hydrogen layer suppresses completely the formation of ordered oxygen superstructures as well as O₂ desorption above 800 K. This occurs with only a 20% reduction in total oxygen coverage as measured by Auger spectroscopy.     

Chlorine chemisorption and surface chloride formation on Au(111)

The adsorption-desorption properties of the gold(111)-chlorine system have been investigated. Thermal desorption experiments following chlorine adsorption at 298 K indicated two desorption processes: the high temperature peak (ΔH = 217 kJmol^?1) showed desorption of equal numbers of molecukr and atomic chlorine species, while the lower temperature peak (ΔH = 140 kJmol^?1) was due to the desorption of Cl₂ only. Chlorine adsorption led to a maximum work function change of +0.5 V and electron-stimulated desorption proceeded with constant cross-section (1.4 × 10¹⁸ cm²), until all chlorine had been removed from the surface These observations are consistent with the immediate formation of a surface chloride (AuCl₃) during chlorine adsorption on Au(111) at 298 K without the intervention of an initial adsorbed overlayer.     

Angle-resolved photoemission study of no chemisorption on Ag(111) surface

An angle-resolved photoemission study using synchrotron radiation has been carried out to investigate the adsorption of NO on Ag(111). At 150 K, NO is adsorbed molecularly on the Ag(111) surface. The NO molecule is found to have an upright orientation from a study using incidence angle dependent measurements and symmetry selection rules. The upright orientation is also confirmed from the study of the shape resonance of the 5σ level. Photon induced dissociation of the chemisorbed NO was observed and is briefly discussed.     

Theoretical study of oxygen chemisorption on (111) and (100) silicon surfaces

The chemisorption of atomic oxygen on (111) and (100) silicon surfaces has been studied by the MNDO method using a cluster approach. The results show that, for both surfaces, chemisorption occurs preferentially on bridge positions, but chemisorption on top positions can play a significant role especially for the (111) surface.     

The structure of benzene on Rh(111): Coadsorption with CO

The molecular structure of benzene coadsorbed with CO on Rh(111) has been investigated by angle resolved UV photoemission (ARUPS), LEED and thermal desorption spectroscopy. The symmetry of the benzene adsorption complex in a mixed benzene-CO (3×3) LEED structure has been determined to C_6v by ARUPS. This indicates that the benzene molecules remain essentially undistorted in the CO coadsorbate layer, as it has been found for the pure benzene layer on Rh(111).     

Methane dissociative chemisorption on Pt(111) explored by microscopic reversibility

Angle-resolved thermal programmed reaction was used to investigate the hydrogenation of methyl radicals on Pt(111). The angular distribution of desorbing methane produced at 240 K was strongly peaked towards the surface normal and the reaction displayed little kinetic isotope effect. When microscopic reversibility arguments are applied, these observations suggest that dissociative chemisorption of CH₄ on an extensively H covered Pt(111) surface will display a sharply angle dependent sticking coefficient and little evidence for tunneling.     

Carbon monoxide induced ordering of benzene on Pt(111) and Rh(111) crystal surfaces

Carbon monoxide induced ordering of an organic molecule, benzene, has been studied on the Pt(111) and Rh(111) crystal surfaces using low-energy electron diffraction, high-resolution electron energy loss spectroscopy, and thermal desorption spectroscopy. We propose detailed geometries for all the ordered structures of coadsorbed CO and benzene. Ordering in the adsorbed overlayer is proposed to result from the interactions between adsorbed CO molecules in the presence of benzene.     

The interaction of oxygen with the Rh(111) surface a

The adsorption of oxygen on Rh(111) at 100 K has been studied by TDS, AES, and LEED. Oxygen adsorbs in a disordered state at 100 K and orders irreversibly into an apparent (2 × 2) surface structure upon heating to T? 150 K. The kinetics of this ordering process have been measured by monitoring the intensity of the oxygen $\text{(1,}\text{1}\text{2}\text{) LEED}$ beam as a function of time with a Faraday cup collector. The kinetic data fit a model in which the rate of ordering of oxygen atoms is proportional to the square of the concentration of disordered species due to the nature of adparticle interactions in building up an island structure. The activation energy for ordering is $\text{13.5 ± 0.5}\text{kcal}\text{mole}$. At higher temperatures, the oxygen undergoes a two-step irreversible disordering (T? 280 K) and dissolution (T?400K) process. Formation of the high temperature disordered state is impeded at high oxygen coverages. Analysis of the oxygen thermal desorption data, assuming second order desorption kinetics, yields values of 56 ± 2 kcal/ mole and 2.5 ± 10^?3 cm² s^?1 for the activation energy of desorption and the pre-exponential factor of the desorption rate coefficient, respectively, in the limit of zero coverage. At non-zero coverages the desorption data are complicated by contributions from multiple states. A value for the initial sticking probability of 0.2 was determined from Auger data at 100 K applying a mobile precursor model of adsorption.     

The geometrical and vibrational properties of the Rh(111) surface

Low-energy electron diffraction (LEED) data have been used to characterize the clean Rh(111) surface. The surface geometry, the degree of surface relaxation, and the Debye temperature have been determined. In the Debye temperature measurement, specular LEED beam intensities were monitored as a function of temperature over a range of electron energies from approximately 30 to 1000 eV. It was found that the bulk Debye temperature is 380 ± 23 K, and the normal component of the Debye temperature at the lowest electron energy used is 197 ± 12 K. The Rh(111) surface relaxation has been determined both by a convolution-transform analysis and by dynamical calculations. Within experimental error, neither expansion nor contraction of the topmost layer has been detected. The results of the convolution-transform analysis of specular beams at two angles of incidence and of a nonspecular beam at normal incidence suggest an expansion of the topmost layer of 3 ± 5% of the bulk layer spacing. In agreement with this, comparisons between the results of the dynamical calculation and experimental data for five nonspecular beams at normal incidence suggest that the surface layer relaxes by 0 ± 5%. In addition, the dynamical calculations indicate that the topmost layer maintains an fcc structure.     

钴原子及其团簇在Rh(111)和Pd(111)表面的扫描隧道显微学研究

利用扫描隧道显微镜和扫描隧道谱(STM/STS)及单原子操纵,系统研究了单个钴原子(Co) 及其团簇在Rh (111)和Pd (111)两种表面的吸附和自旋电子输运性质. 发现单个Co原子在Rh (111)上有两种不同的稳定吸附位,分别对应于hcp和fcc空位, 他们的高度明显不同,在针尖的操纵下单个Co原子可以在两种吸附位之间相互转化. 在这两种吸附位的单个Co原子的STS谱的费米面附近都存在很显著的峰形结构, 经分析认为Rh (111)表面单个Co原子处于混价区,因此这一峰结构是d轨道共振 和近藤共振共同作用的结果.对于Rh (111)表面上的Co原子二聚体和三聚体, 其费米面附近没有观测到显著的峰,这可能是由于原子间磁交换相互作用 和原子间轨道杂化引起的体系态密度改变所共同导致.与Rh (111)表面不同, 在Pd (111)表面吸附的单个Co原子则表现出均一的高度.并且对于Pd (111)表面所有 单个Co原子及其二聚体和三聚体,在其STS谱的费米面附近均未探测到显著的电子结构, 表明Co原子吸附于Pd (111)表面具有与Rh (111)表面上不同的原子-衬底相互作用与自旋电子输运性质.     

Co desorption and adsorption on Pt(111)

The kinetics of the desorption of CO from a Pt(111) crystal between 419 and 505 K is reported using a Low-Energy Molecular-Beam-Scattering (LEMS) technique with a helium probe beam and a CO dosing beam. The resulting first-order Arrhenius rate constant is $\text{k = 2.7 × 10}{}^{13}\text{exp(?31.1}\text{kcal}\text{mole}\text{· RT) s}{}^{\mathrm{?1}}$. We also report a study of the equilibriumadsorbed CO between 400 and 600 K using LEMS. These results, fitted to a Temkin isotherm model, indicate that the adsorption energy decreases linearly with surface coverage with the average value equal to $\text{31.1 + 1.2}\text{kcal}\text{mole}$ over the coverage range 0 < θ ? 0.5. The average harmonic oscillator frequency of the adsorbed CO molecules is 191 ± 76 cm^?1.