Nickel carbonyl adsorption on the Ni(111) surface

Overlayers formed by the adsorption of Ni(CO)₄ in CO on the Ni(111) surface at 100 K were characterized using high resolution electron energy loss spectroscopy and thermal desorption spectroscopy. At temperatures below 135 K, molecular nickel carbonyl adsorbs on the CO saturated Ni(111) surface as suggested by several observations. Vibrational transitions characteristic of molecular Ni(CO)₄ are dominant. The energy dependence of both the elastic and inelastic electron scattering cross sections are dramatically altered by Ni(CO)₄ adsorption. All of the mass spectrometer ionization fragments typical of molecular Ni(CO)₄ are observed in the narrow thermal desorption peak at 150 K. The inelastic scattering cross sections for both adsorbed nickel carbonyl and adsorbed CO on the Ni(111) surface suggest that a nonresonant dipole scattering mechanism is dominant.     

Scattering of He atoms from rough surfaces

Three diverse rough surfaces have been studied using inelastic He scattering. The first is an ion bombarded Ag(110) surface where a broadened specular peak remains visible but scattering remains entirely elastic as viewed by the incoherent component. The second is a cleaved Te(10 ) surface composed of helical chains where the roughness originates from thermal oscillations and scattering is almost entirely inelastic. Thirdly, a glass (7740) disc is shown to be physically rough but the surface is sufficiently rigid to yield largely elastic incoherent scattering.     

Direct time-domain observation of ultrafast dephasing in adsorbate-substrate vibration under the influence of a hot electron bath: Cs adatoms on Pt(111)

The stretching vibration of Cs adsorbed on Pt(111) is excited coherently by resonant stimulated Raman excitation and its time evolution is probed by fs time-resolved second harmonic generation as a function of pump laser fluence I. As I increases, a fast dephasing component with the lifetime of tau=0.7 ps grows, being superimposed on a slow one with tau=1.9 ps. The fast component is a manifestation of pure dephasing caused by elastic and inelastic scattering of hot electrons at adsorbate.     

Temperature dependence of Pt(111) surface relaxation

A careful investigation of the Pt(111) surface has been carried out, using the MeV heliumscattering technique. The anomalously large surface relaxation effect reported previously has been identified as an experimental artifact resulting from an unexpectedly large surface damage effect at low temperature. Optimum conditions have been established for minimizing the main experimental sources of error: background subtraction, radiation damage, and deviations from the Rutherford scattering law. Using these optimum conditions, a series of scattering measurements has been made over the temperature range 40–300 K. At all temperatures, we observe a significant anisotropy in the 〈111〉 angular scans, indicating an outward relaxation of the Pt(111) surface plane. By comparing this observed anisotropy with a set of Monte Carlo simulations, a value of 0.03 ? 0.01 Å (i.e. 1.3 ? 0.4%) is obtained for the surface relaxation. The temperature dependence of the surface peak also indicates that the enhanced vibrational amplitude of the surface atoms is not nearly as large as had been derived previously from high-temperature LEED studies.     

The adsorption of hydrogen and the reaction of hydrogen with oxygen on Pt (100)

The adsorption of hydrogen on Pt (100) was investigated by utilizing LEED, Auger electron spectroscopy and flash desorption mass spectrometry. No new LEED structures were found during the adsorption of hydrogen. One desorption peak was detected by flash desorption with a desorption maximum at 160 °C. Quantitative evaluation of the flash desorption spectra yields a saturation coverage of 4.6 × 10¹⁴ atoms/cm² at room temperature with an initial sticking probability of 0.17. Second order desorption kinetics was observed and a desorption energy of 15–16 kcal/mole has been deduced. The shapes of the flash desorption spectra are discussed in terms of lateral interactions in the adsorbate and of the existence of two substates at the surface. The reaction between hydrogen and oxygen on Pt (100) has been investigated by monitoring the reaction product H₂O in a mass spectrometer. The temperature dependence of the reaction proved to be complex and different reaction mechanisms might be dominant at different temperatures. Oxygen excess in the gas phase inhibits the reaction by blocking reactive surface sites. At least two adsorption states of H₂O have to be considered on Pt (100). Desorption from the prevailing low energy state occurs below room temperature. Flash desorption spectra of strongly bound H₂O coadsorbed with hydrogen and oxygen have been obtained with desorption maxima at 190 °C and 340 °C.     

X-ray photoelectron diffraction investigation of the (2 × 2) overlayers of Cs and K on Cu(111)

X-ray photoelectron diffraction measurements have been made for the Cu(111)(2 × 2)-Cs and Cu(111)(2 × 2)-K systems to explore the possibility of using substrate emission XPD for the elucidation of adsorbate-substrate registry in these cases of strongly scattering adsorbate atoms and anticipated atop adsorption sites. Although scattering effects within the substrate, for sub-surface emitters, clearly complicate the interpretation of the data, simple symmetry arguments do give substantial support to the identification of atop adsorption sites in both systems.     

Angular dependence of auger electron emission from Cu (111) and (100) surfaces

Experimental angular emission profiles of the M_2,3M_4,5M_4,562 eV Cu Auger electrons from clean copper (100) and (111) surfaces in several azimuths are presented. A simple single scattering theory to account for elastic scattering of the Auger electrons by other ion cores in the solid is presented, and calculations have been performed to assess the importance of this process in contributing to the observed angular dependence. These calculations produce angular structure having a similar magnitude and temperature dependence to that observed experimentally, and some featural similarity in peak positions or shapes. It appears that elastic scattering is an important source of angular dependence, and that studies of adsorbed species on surfaces should provide a very sensitive method of surface structure determination.     

ESR and TPD Investigations of the Adsorption of Di-tert-butyl Nitroxide on Au(111) and NiO(111). Evidence for Long-Range Interactions

Electron spin resonance and temperature-programmed desorption spectra of thin layers of DTBN (di-tert-butyl nitroxide) adsorbed on Au(111) and NiO(111)/Au(111) surfaces have been measured. The temperature-programmed desorption data show a weak chemisorption of the DTBN molecules in the monolayer on both surfaces. On Au(111) as well as on NiO(111)/Au(111), the ESR signal from monolayer coverages is totally suppressed. This suppression continues into the multilayer regime on both substrates. Disturbances of the substrate/adsorbate interface have a strong influence on the range of the signal suppression. Possible reasons for this behavior are discussed.     

Growth and crystalline structure of Co layers on Cu(0 0 1)

The crystalline structure of Co layers deposited on the Cu(0 0 1) surface was investigated with the use of the directional elastic peak electron spectroscopy (DEPES). For clean Cu(0 0 1) the experimental DEPES profiles obtained for different energies of the primary electron beam exhibit intensity maxima corresponding to the close packed rows of atoms. The Auger peak kinetics recorded during continuous Co deposition suggest the layer-by-layer growth mode. The DEPES profiles recorded for 10 monolayers (ML) of Co on Cu(0 0 1) reflect a short-range order in the adsorbate. Intensity maxima observed in the DEPES profiles for Co along [1 0 0], [0 1 0], and [1 1 0] azimuths of Cu(0 0 1) are characteristic of the face centered cubic (fcc) Co(0 0 1) layers. Low-intensity reflections and considerable background intensities were found in the low energy electron diffraction (LEED) patterns recorded from 10 ML of Co, which indicates a weak long-range order in the adsorbate. The adsorption of about 20 ML of Co results in considerable background contribution to DEPES. No reflections but a large background were observed with the use of LEED for this layer. The heating of the Co/Cu(0 0 1) system at T = 770 K leads to an increase of the short- and long-range order in the overlayer, observed in the DEPES profiles and LEED patterns, respectively. The theoretical DEPES profiles were obtained with the use of a multiple scattering approximation. A very good agreement between experimental and theoretical scans was found for the clean and covered copper substrate. The latter proves the epitaxial growth of Co layers on Cu(0 0 1).     

Local bond breaking via STM-induced excitations: the role of temperature

We discuss the influence of temperature on local bond breaking through multiple vibrational excitations induced by inelastic tunneling in the STM. We focus on hydrogen desorption from the H---Si(111) and H---Si(100) systems, but the results are general. The substrate temperature affects the desorption yield in two important ways: first, lowering the temperature increases the H---Si vibrational energy relaxation time, resulting in a higher effective adsorbate temperature and an increased desorption yield. Second, lowering the substrate temperature decreases the dephasing rate of the H---Si modes (manifested by a decrease of the infrared absorption linewidth), which then reduces the rate of incoherent (Förster) vibrational energy transfer away from the Stark-shifted H---Si mode under the tip. This increases the localization of the vibrational energy and enhances the probability for multiple vibrational excitation and desorption. Finally, we discuss the possible implications of our findings on the mechanism of MOS device degradation by hot electrons.     

Combined nuclear-molecular resonance inelastic scattering of x rays

We report on theoretical and experimental studies of nuclear inelastic scattering in a molecular crystal, whose atoms experience both molecular and lattice vibrations. In this case scattering proceeds as combined nuclear-molecular resonance inelastic scattering. The lattice vibrations give rise to inelastic scattering around the molecular resonances with an energy dependence identical to that around the nuclear resonance. The incoherent nature of the scattering in the molecular resonances results in a proper balance of elastic and inelastic components, which has important implications for studies of heterogeneous systems.     

A contribution to the investigation of ion impact desorption by ion scattering

Sputtering or ion impact desorption of adsorbed layers can be directly investigated by low-energy ion scattering. Because of its specific sensitivity to surface atoms, this method provides the possibility of monitoring the decrease of the signal from the adsorbate or the increase of the signal from the substrate. Both signals were studied with He⁺ backscattering from the system O on Ni (110). The measured desorption cross-sections and the principal implications for both ways of observation are discussed. The use of the substrate signal for the desorption study can be of major advantage, particularly in the case of light adsorbates.     

Effect of superradiance on transport of diffusing photons in cold atomic gases

We show that in atomic gases cooperative effects like superradiance and subradiance lead to a potential between two atoms that decays like 1/r. In the case of superradiance, this potential is attractive for close enough atoms and can be interpreted as a coherent mesoscopic effect. The contribution of superradiant pairs to multiple scattering properties of a dilute gas, such as photon elastic mean free path and group velocity, is significantly different from that of independent atoms. We discuss the conditions under which these effects may be observed and compare our results to recent experiments on photon transport in cold atomic gases.     

The adsorption of oxygen on the stepped Pt(S)-[9(111) × (111)] face

The adsorption of oxygen on the stepped Pt(S)-[9(111) × (111)) face has been studied by flash desorption, LEED and AES. On adsorbing oxygen the (1 × 1) LEED pattern of the clean face was transformed into a (2 × 2) pattern. A lower limit of the initial sticking coefficient of 0.06 and a saturation coverage of approximately 0.5 monolayer were determined. The flash desorption spectra exhibited two not completely resolved desorption maxima. From the peak temperatures the activation energies of desorption were estimated to be 41 and 49 kcal/mole. Under the same experimental conditions some experiments were done on a smooth (111) Pt face. However, the results did not differ significantly from those obtained on the stepped surface. In addition on the smooth (111) face the adsorption of oxygen activated in a high frequency discharge was studied. Oxidation was not observed beyond the chemisorption layer which is formed from molecular oxygen.     

Adsorption studies on a stepped Pt(111) surface: O2, CO,C2H4, C2N2

A comparative study of the adsorption of several gases on a Pt(S)-[9(111) × (111)] surface was performed using LEED, Auger spectroscopy, flash desorption mass spectrometry and work function changes as surface sensitive techniques. Adsorption was found to be generally less ordered on the stepped surface than on the corresponding flat surface with the exception of the oxygen, where r well ordered overlayer in registry over many terraces was found. Absolute coverages were determined from flash desorption experiments for O₂, CO and C₂N₂. Similar values were obtained as on flat Pt surfaces. Two different surface species seem to be formed upon adsorption of C₂H₄ depending on the adsorption temperature. Contrary to reports from Pt(111) surfaces conversion between the two surface species is heavily restricted on the stepped surface. Work function changes revealed nonlinear adsorbate effects where the adsorbate is electronegative with respect to the substrate. Various adsorption models are discussed in the light of complementary experimental evidence. The results of this study are compared with data available from flat Pt surfaces and possible influences of steps are discussed. No general trends, however, emerge from this comparison and it seems that eventual influences of steps have to be considered individually for every adsorbate.     

The adsorption of activated nitrogen on platinum single crystal faces

The adsorption of activated nitrogen on a stepped Pt(S)-[9(111) × (111)] face was investigated by LEED, AES and flash desorption. Nitrogen was supplied to the crystal from a high frequency discharge tube. For comparison some orienting measurements were also carried out on smooth (111) and (100) platinum faces. Activated nitrogen is adsorbed at room temperature on all three faces up to about half a monolayer coverage. No additional LEED patterns indicating long range order of the adsorbed layer were found. By flash heating a small desorption peak at 120°C and a large peak between 175 and 230°C depending on the initial coverage were observed on the (111) type faces. The desorption can be described approximately by a second order rate law with an energy of activation of 25± 3 kcal/mole. No influence of surface steps on the properties of the adsorbed layer was detected. On the (100) face two coverage independent desorption maxima at 120 and 170°C of about equal intensities were found.     

Surface structure from angular dependence of auger electron emission

Auger electrons emitted from atoms in the vicinity of a solid surface can show strong angular dependence in their emission due to elastic scattering from the surrounding ion cores of the solid. Model calculations for the emission of Auger electrons from sulphur adsorbed on a Ni (100) surface show that these angular features are very sensitive to the adsorption site of the emitting atoms, and that a study of these effects should produce a method of surface structure analysis for the location of preferred surface adsorption sites. This approach would appear to be an improvement over LEED because of its high sensitivity to structural changes and because it does not require long range order in the adsorbate layer.     

Effects of adsorbates on electron spin polarization in low energy electron diffraction from tungsten (001): I. Disordered CO and O2 overlayers

Electron spin polarization and intensity profiles have been measured in low energy electron diffraction (LEED) for the (00) beam at θ = 13δ and ø = 0δ from W(001) as a function of surface exposure to CO and O₂. Significant changes have been observed in the profiles upon exposure to both adsorbate gases, and the implications of these results are discussed.     

Diffusion effects on thermal desorption spectra of hydrogen from (111) surfaces of diamond-type crystals

We study the thermal desorption of atoms located in subsurface interstitial sites at the (111) surface of crystals with a diamond-type structure. From these sites they may either desorb or diffuse deeper into the crystal. A set of master equations is set up to describe the resulting random walk problem, and its solution yields both the desorption rate and total desorbed amount, as a function of time for constant temperature thermal desorption, or of temperature for flash desorption with a constant heating rate. Unequal values of the desorption and diffusion probabilities are allowed and the effect of initial occupation of deeper interstitial sites as well, is considered. In the latter case the desorption rate curve shows a double peak when the probabilities favour desorption, and in all cases a distinct long time or high temperature tail of the peak is found to result from diffusion. Based on this study, a model of H adsorption on Si(111) is presented and shown to explain several features of the experimental results of Schulze and Henzler.     

Inelastic scattering of He atoms from a Cu(110) surface

A He beam has been used to measure inelastic scattering from a Cu(110) surface. The scattering was a result of predominantly single phonon events and both energy gain and loss processes were observed. This was in contrast to Cu(001) where only energy loss was observed. For Cu(110), aligned in the [001] azimuth, partial dispersion relations have been measured which meant that phonons with ΔQ values up to the zone boundary value have not been detected under the present experimental conditions. The elastic incoherent component varied with azimuthal angle for Cu(110).