New feature in the Auger peak of adsorbed oxygen

Recent joint theoretical and experimental investigations of Auger core-core-valence spectra of alkali adatoms on simple metals have revealed that such technique is capable to ascertain contributions from different adsorption environments in the signal [M.I. Trioni, S. Caravati, G.P. Brivio, L. Floreano, F. Bruno, A. Morgante, Phys. Rev. Lett. 93 (2004) 206802]. Consequently, to verify if such an effect is present also for other chemical species, we study theoretically the KLV transition of oxygen either as a bulk impurity or as an adsorbate in/on Al and Ag (jellium-like). We make use of the Fermi golden rule in which the matrix elements of the interaction are calculated within DFT. We verify that the relevant physical quantity of this phenomenon is the excited local density of states (LDOS), calculated within a region centered on the core ionized atom. The Auger rate for oxygen in Ag bulk displays a single asymmetric peak, while for adsorbed oxygen a second smaller feature at lower energies, and very close to the first one, appears. This unexpected result follows from the removal of the degeneracy of the m quantum number of the 2p states of oxygen at the surface. It is only displayed on the electronically less dense metal (Ag), but not on Al.     

An Auger and X-ray photoelectron spectroscopic study of sodium metal and sodium oxide

Photoelectron and Auger electron measurements have been made on polycrystalline films of sodium metal evaporated in ultra high vacuum, and on Na₂O produced by in-situ oxidation by dry oxygen. Most of the spectra were recorded using Mg Kα (1254 eV) radiation but excitation by 5 keV electrons or monochromatized Al Kα (1487 eV) X-rays was used for specific purposes. Core and valence electron binding energies, photoionization cross-sections relative to Na 1s, KLL and KLV Auger energies and transition probabilities are reported. Energy losses in the metal and oxide are discussed and the relative intensities of surface and bulk plasmon losses have been used to calculate mean electron escape depths in the metal. When corrections were made for experimental geometry, escape depths of 10 Å at 180 eV and 31 Å at 1200 eV were obtained. An escape depth of 23 Å at 980 eV was obtained by Na 1s-Na K-Auger intensity correlation and this is consistent with the plasmon data. Data on Auger satellite lines are presented and, in particular, evidence has been obtained which indicates that a high energy satellite should not be attributed to a plasmon gain mechanism. Valence band influences on the KLV Auger spectra are discussed with reference to the XPS spectrum and other sources of valence band information. Unexpected structure was found in the KLV spectra of the metal which, pending thorough interpretation, offsets the sensitivity and resolution advantages which these spectra otherwise offer for valence band studies.     

Auger electron spectroscopy of cesium adsorbed on clean and oxygen covered (100) tungsten

Auger electron spectroscopy of cesium adsorbed on clean W(100) shows that the well known N_4,5O_2,3O_2,3 peak can be resolved into three peaks at 43–45.8 and 48.4 eV. Simultaneously as well defined peak appears at 62 eV and it is shown that this transition involves ionization of the N₄N₅ cesium level. An additional peak appears at 56.5 eV as cesium adsorbs on a previously oxygen-covered W(100) surface. Its existence is discussed and might indicate that oxygen valence electrons are involved in this new transition.     

A RHEED study of oxygen adsorbed on copper

The effect of oxygen adsorption on various clean, stepped copper surfaces at 300°C was examined by the use of Reflection High Energy Electron Diffraction (RHEED). The stability of a few high index planes is considered and the idea of this enhanced stability being due to a “fit” between the adsorption structure and the terrace width was extended. The interpretation of RHEED patterns from faceted surfaces was discussed so as to account for such features as the curving of the rods and the apparent existence of extra rods.     

X-ray study of molecular oxygen adsorbed on graphite

We have performed a detailed X-ray diffraction study of O₂ adsorbed on UCAR-ZYX and Le Carbon Lorraine vermicular exfoliated graphite between 15 and 50 K. At least four phases of physisorbed oxygen are found. The monolayer δ phase consists of a centered parallelogram lattice, with the molecular axes parallel to the graphite surface. The data are consistent with a triple point at 26 K. The melting transition at a coverage of one monolayer appears to be first order. At higher coverages the molecules undergo a lying-down to standing-up transition; the higher coverage ζ phase froms an approximately triangular lattice with the molecular axes perpendicular to the graphite surface. Satellite peaks around the (1, 0) Bragg peak indicate, however, that this cannot be a simple triangular lattice; possible explanations include successively incommensurate layers or a sinusoidal density modulation. For coverages in the two-layer region the ζ phase modulation peaks disappear at 37 K, and at 40 K the adsorbed oxygen appears to undergo a first order melting transition into a fluid phase. With increasing coverage, the 2D X-ray diffraction profiles and phase boundaries do not connect smoothly onto those of the 3D α and β phases. At low temperatures (T < 30 K) the ζ phase always coexists with bulk crystallites; for temperatures near the 2D melting transition the 3D peaks are not observable. These data, taken together with the heat capacity results, suggest a wetting transition with only the bilayer lamellar phase or bulk O₂ being stable at low temperatures.     

IR reflection-absorption spectroscopy of CO adsorbed on palladium

Kinetic theory is used to compute the flux and relative translational kinetic energy incident upon a surface oscillating in a rarefied gas. The flux incident upon the oscillatory surface is deficient in low-velocity molecules from the gas during the reentry half of a vibration cycle, in which the surface moves into the gas, because all molecules which are to strike the oscillatory surface from the gas must cross the plane of maximum surface extension during that cycle. The deficiency is largely compensated for by recapture, during the reentry half of a cycle, of low-velocity molecules emitted during the recession half of the cycle. The result of these two opposing effects is that the average energy of gas-surface collisions, and therefore the temperature rise of an oscillatory surface is greater than that of a constant speed plate of the same rms velocity in the same gas. For argon at 300 K and 10^?3 torr incident upon a surface with an rms velocity of 3.3 × 10³ cm sec^?1 the apparent average temperature of incident molecules is 302.91 ° for an oscillatory surface and 302.63 ° for a constant speed plate. Measurements of the temperature rise of an oscillatory surface offer a way to measure thermal accomodation coefficients.     

LEED,Auger and work function study of iodine adsorbed on W(110)

The adsorption of iodine on a W(110) surface has been studied by LEED, Auger and work function changes. LEED has revealed several phases which desorb in different temperature regimes and are accordingly designated γ, α, β₁, β₂, and β₃. The γ and α phases exhibited p(2 × 2) and p(2 × 1) surface nets respectively with coherently positioned antiphase boundaries which produced a splitting of selected LEED beams. The separation between the antiphase boundaries of the α phase increased with decreasing coverage. Both the γ and α phases were associated with molecularly absorbed iodine. The three β phases were associated with dissociatively adsorbed iodine which formed chain structures on the surface with the arrangement of iodine atoms within each chain being unique to the particular phase. Continuous changes in coverage then occurred by sheets of these chains shearing to produce packing faults at the resulting shear lines. This shearing process occurred coherently in the β₁ and β₃ phases and incoherently in the β₂ phases. In the former cases, the effect was seen by the continuous movement of coherent LEED beams with changing coverage. A phase diagram was constructed to describe the relative coverages and thermal stability of the phases. The characteristic Auger electron emission of iodine was observed at 495 eV and used to estimate the surface coverage. The work function was found to decrease by 0.4 eV with the adsorption of the first half monolayer and remained unchanged with further adsorption.     

Photoemission study of oxygen adsorbed on coldly deposited silver films

UPS spectra of coldly deposited silver films differ from those of films deposited at room temperature by electronic states localized at surface defects with an energy about 4.2 eV below E_F. Changes after exposure at 140 K to oxygen only occur in the presence of these defects, demonstrating that oxygen is only adsorbed at defects. Raman vibrational spectroscopy shows that oxygen is adsorbed nominally as O₂^? and O₂^2?. Possible assignments of the oxygen related UPS structures are discussed.     

CO2在Pd表面吸附的热力学

 用密度泛函方法和相对论有效原子实势,分别对PdCO₂,PdCO和PdH的基态几何构型进行优化, 得到PdCO₂分子基态为Cs构型, Pd与CO2分子在同一平面, 键长PdC为0.203 0 nm, CO为0.118 3 nm, CO′为0.121 0 nm, 键角∠OCO′为154.215°,电子状态为1A′; PdCO分子基态电子状态为1+, 键长PdC为0.183 4 nm, CO为0.114 0 nm, 键角∠PdCO为180°; PdH分子基态为2∑, 键长PdH为0.152 6 nm。根据电子-振动近似理论计算了不同温度下金属Pd 与CO₂,CO及H2分子反应的生成热力学函数, 导出了反应平衡压力随温度的变化关系。分析认为杂质CO₂气体引起Pd合金膜中毒可能是由于CO₂分子吸附在Pd膜表面,形成Pd的CO₂化合物后,再自发分解为PdO和CO,而使Pd表面出现O和CO中毒所致。     

Auger spectroscopic study of the surface composition of Pt/Sn alloys in ultrahigh vacuum and in the presence of oxygen and hydrogen

The surface composition of two Pt/Sn alloys, viz. PtSn and Pt₃Sn, has been followed by means of AES, as a function of annealing in ultrahigh vacuum, oxygen chemisorption and reduction with hydrogen.The results, which were quantitatively interpreted with the aid of a novel calibration technique, reveal the following features: - The surface of PtSn and Pt₃Sn becomes enriched with tin by annealing in vacuum. Ultimate values of 68±5 at% Sn for PtSn and 41±5 at% Sn for Pt₃Sn were attained after annealing at 500°C. - The adsorption of oxygen on the annealed surface of PtSn and Pt₃Sn causes a further enrichment with tin, while severe oxidation of PtSn at 500°C leads to complete disappearance of Pt from the surface. - Oxygen is more strongly and differently bound on a surface containing about 40 at% Sn than on a surface containing about 70 at% Sn. Activated adsorption of oxygen takes place only on the latter. The results suggest the formation of SnO₂ surface complexes on the exposed surface of Pt₃Sn. - Reduction of the alloys at 500°C carries the excess of tin into the bulk and reduces its surface concentration to 35±5 at% for Pt₃Sn and 64±5 at% for PtSn, which is an enrichment of the surface with platinum relative to the annealed state.     

Infrared spectroscopic study of alkyl aldehydes adsorbed on cations supported by layer silicate

The self-supported film specimen of Wyoming montmorillonite as a layer silicate exchanged by cations, Li⁺, Na⁺, K⁺, Ca²⁺, Ni²⁺, and Al³⁺ were allowed to contact acetaldehyde, acrolein and crotonaldehyde within the heatable gas cell. Adsorption mechanism of alkyl aldehydes on cations supported by layer silicate was studied by means of infrared spectroscopy and X-ray. The infrared spectra between 4000 and 1200 cm⁻¹ at different pressures of adsorbates indicated bond formation through carbonyl oxygen. The intensity of the stretching OH was analyzed and resonance form of cationic hydroxyl was proposed as an adsorption site. The carbonyl stretching band, which shifted about 130 cm⁻¹ to lower frequencies was observed only for Ni²⁺, Ca²⁺, and Al³⁺ supported by layer silicate and was attributed to >CO···Mⁿ⁺ complex formation. A sharp band, which appeared as a shoulder at 1722 for acetaldehyde and 1690 for acrolein and crotonaldehyde, was responsible for the interaction of carbonyl with surface hydroxyl. The second broad band, which appeared at about 1710-1660, was responsible for hydrogen bonding between carbonyl oxygen and cationic hydroxyl group.     

An experimental and theoretical kinetic study of t-butyl radical reaction with molecular oxygen

In this work, a unifying picture of the kinetics of the t-C₄H₉ + O₂ reaction is presented by combining the current and previous experimental results with theory. Direct, time-resolved experiments were performed over a wide temperature range (200–500 K) at low pressures (0.3–6 Torr) using a photoionization mass spectrometry method. The kinetic measurements of the t-butyl + O₂ reaction were initiated by laser photolysis of pinacolone at 193 nm or t-butyl bromide at 248 nm to produce t-C₄H₉ radicals. Energies calculated by quantum chemistry at the CCSD(T)/CBS and CASPT2/CBS levels of theory were used in master equation simulations of the kinetics of the t-C₄H₉ + O₂ reaction. The calculations successfully reproduce the pressure and temperature dependencies of both the current low-pressure experiments and literature kinetic data at about atmospheric pressure as well as the literature kinetic data for the overwhelmingly most important bimolecular reaction channel, t-C₄H₉ + O₂ → i-C₄H₈ + HO₂ in the intermediate temperature range. The experimentally constrained master equation model was utilized to simulate the t-C₄H₉ + O₂ reaction kinetics over wide range of conditions. The results of these simulations are provided in ChemKin compatible PLOG format for later use.     

Auger electron spectroscopic study of CO2 adsorption on Zircaloy-4 surfaces

We investigate the adsorption of CO₂ onto Zircaloy-4 (Zry-4) surfaces at 150, 300 and 600 K using Auger electron spectroscopy (AES). Following CO₂ adsorption at 150 K the graphitic form of carbon is detected, whereas upon chemisorption at 300 and 600 K we detect the carbidic phase. As the adsorption temperature is increased, the carbon Auger signal increases, whereas the oxygen signal decreases. Adsorption at all three temperatures results in a shift of the Zr Auger features, indicating surface oxidation. The effect of adsorbed CO₂ on the Zr(MVV) and Zr(MNV) transitions depends on adsorption temperature and is less pronounced at higher temperatures. On the other hand, changes in the Zr(MNN) feature are similar for all three adsorption temperatures. The changes in the Zr Auger peak shapes and positions are attributed to oxygen from dissociated CO₂, with the differences observed at various temperatures indicative of the diffusion of oxygen into the subsurface region.     

Oxygen KLL Auger spectra from O2 and CO adsorbed on Ni

High resolution oxygen KLL Auger spectra from O₂ and CO adsorbed on clean Ni (110) have been measured and compared. These Auger spectra are quite different from one another and are compared with spectra of the free molecules. Similarities between the oxygen spectra from adsorbed and gaseous CO are noted and interpreted as due to the weak bonding of CO to Ni with the O atom furthest from the surface. These Auger studies also characterize the change in bonding of adsorbed CO due to electron beam interaction.     

Shapes and shifts in the oxygen Auger spectra

The oxidation of silicon and platinum single crystal faces, of polycrystalline supported catalysts and of some alloy surfaces has been studied by AES and as far as possible by LEED. A comparison of the oxygen Auger spectra obtained during the oxidation process with those found on oxides has been made; it shows that the modification of the fine structure of the oxygen Auger peaks gives some information about the binding state of oxygen. Two different structures, which compete one with the other, are described. In one case, a spectrum where three lines dominate is obtained; in the other case, a “quasi-atomic” spectrum characterized by five features is observed: multiplet splitting in the two-hole final state is predominant. Besides these differences in the fine structure of the Auger spectra one can notice shifts of several eV for the main feature. They have been correlated with the various observed LEED patterns. Physisorption, chemisorption, solution of oxygen in the metal lattice, growth of ordered or amorphous oxides are the different possibilities which are discussed.     

Effect of adsorbed oxygen on the properties of ytterbium nanofilms

The effect of O₂ molecules adsorbed on the surface of ytterbium nanofilms on the properties of the volume and surface of these films has been studied. It has been shown that the dependence of the work function of the films on the concentration of O₂ adsorbed molecules exhibits a nonmonotonic behavior: originally, the work function decreases, to start increasing again on passing through a minimum. At high oxygen doses, this increase stops. Adsorption of oxygen brings about a fundamental rearrangement of the Auger spectra of ytterbium; indeed, the Auger peaks observed before oxygen adsorption disappear completely after its deposition on the surface, to become replaced by other ones. The results obtained qualitatively agree with similar observations amassed by the present authors in studies of adsorption of CO molecules on the surface of ytterbium films. These results should be ascribed to a manifestation of complex processes of electron exchange between these films and adsorbed O₂ molecules. These processes end up in a qualitative rearrangement of the electronic structure of the part of film volume that borders the surface, where ytterbium transforms into the d metal.