Electronic excitations on clean and adsorbate covered Pd(111) by angle resolved electron energy loss spectroscopy

Electronic excitations on clean and adsorbate covered Pd(111) have been investigated by angle resolved electron energy loss spectroscopy. Primary energies in the range of 50–1000 eV were chosen for strong specular reflection to emphasize elastic diffraction-before-loss processes. The clean Pd spectra are compared with optical data, and good correspondence is found for the optical limit (q ? 0). The loss features are interpreted in terms of plasmon resonances and interband transitions within the framework of a recent band structure calculation. Virtually no dispersion is observed for the intrinsic Pd losses, but vertical interband transitions decay fast in the dispersive (q ≠ 0) spectra. Two adsorbate systems are investigated in this study: CO in a disordered adsorbate layer and bromine in a well-ordered $\text{(}\text{3×}\text{3 )R30°}$ structure. Adsorbate derived loss features are generally prominent in the nonspecular (q ≠ 0) spectra. While no dispersion is seen for the intramolecular 13.5 eV excitation of adsorbed CO, dispersion up to 1 eV is found for the Br 4p derived loss feature of the ordered overlayer. This is discussed in terms of a two-dimensional adsorbate band structure of bromine.     

Angular dependence of the electron energy loss spectra from a clean and adsorbate covered W(001) surface

A dispersion analysis of the EELS from a W(001) surface in the range 1 < ΔE < 35 eV has been performed and compared with recent and complete optical data for tungsten. The non-dispersive (k ～ 0) EELS correlated well with a combination of the surface and bulk loss functions calculated from the optical data. Losses at 1–5 eV and a pair at 32 and 34.5 eV were assigned to interband and N_6,7 core ionization excitations respectively. The principal bulk and surface plasmon losses were identified at 24.0 and 20.3 eV respectively. Two further losses at 14.0 and 9.6 eV were also observed and assigned to subsidiary plasmon losses. All four plasmon losses showed only minimal energy dispersion, never exceeding 1.5 eV. A momentum selectivity for separating bulk and surface interband losses was demonstrated with the non-dispersive losses arising from excitations within the bulk even with incident energies as low as 88 eV, whereas their dispersive counterparts were extremely sensitive to the chemical state of the surface. New adsorbate derived losses which develop during adsorption were associated with excitations from the new deep lying adsorbate levels to final state levels at or near the Fermi level. It was concluded that this final state was also responsible for the N_6,7 ionization losses.     

Theoretical treatment of excited electronic states of adsorbates on metals: Electron attachment to CO2 adsorbed on Pt(1 1 1)

Photochemistry involving adsorbates on metals often proceeds by photoexcitation of the metal followed by transient attachment of photoemitted electrons to the adsorbate. First principles theoretical methods suitable for describing electronic states embedded in a near continuum of metal to metal excitations are described and an application to electron attachment to CO₂ adsorbed on Pt(1 1 1) is reported. Wavefunctions are constructed by ab initio configuration interaction methods which allow a rigorous resolution of states and differentiation between competing pathways of molecular desorption and dissociation. An embedding theory is used to achieve high accuracy in the adsorbate-surface region. The energy required to form the electron attached state is 5.2 eV for excitation to bent CO₂ and 6.8 eV for excitation to linear CO₂, hence both energies are near the work function of the metal (5.7 eV). The process also involves localization of the metal hole and attraction of the charged adsorbate to the metal. Optimum geometries are calculated and pathways that results in desorption, dissociation by bond rupture directly in the excited electronic state, or dissociation after return to the ground state potential energy surface via vibrational processes are explored.     

Adsorbate band structure of bromine on Pd(111) studied by angle resolved ultraviolet photoemission

The photoemission spectra from Pd(111) and from the Pd(111)-Br(√3 × √3)R30° system are reported; some new features for the clean surface are detected and assigned. The principal effect of the Br overlayer on the direct transitions is a general intensity reduction. Three adsorbate derived features are detected; one at 4 eV with no dispersion is probably an adsorbate-induced feature of the metal, and the other two which disperse are assigned as Br 4p_x, (4.5 eV) and Br 4p_z (6 eV) at $\text{}\text{?}$gG.     

The adsorption of oxygen and carbon monoxide on cleaved polar and nonpolar ZnO surfaces studied by electron energy loss spectroscopy

Electron energy loss spectroscopy (ELS) with primary energies e₀ ? 80 eV has been performed on ultrahigh vacuum (UHV) cleaved nonpolar (11?00) and polar zinc (0001) and oxygen (0001?) surfaces of ZnO to study the adsorption of oxygen and carbon monoxide. Except for CO on the nonpolar surface where no spectral changes in ELS are observed a surface transition near 11.5 eV is strongly affected at 300 K on all surfaces by CO and O₂. At 300 K clear evidence for new adsorbate characteristic transitions is found for oxygen adsorbed on the Zn polar surface near 7 and 11 eV. At 100 K on all three surfaces both CO and O₂ adsorb in thick layers and produce loss spectra very similar to the gas phase, thus indicating a physisorbed state.     

Electron spectroscopy of surfaces by impact of metastable He atoms: CO on Pd(110)

Deexcitation of metastable He1 2¹S (excitation energy E1 = 20.6 eV) or 2³S (E* =19.8 eV) atoms at a clean Pd(110) surface proceeds through a two-stage process (resonance ionization + Auger neutralization, RI + AN). The measured electron energy distribution reflects the self-convolution of the local density of states of the outmost atomic layer. A CO adlayer suppresses the RI step and the spectra are caused by Auger deexcitation (Penning ionization). Comparison with corresponding UPS data allows identification of the valence orbitals of the adsorbate. Emission up to the Fermi level is ascribed to contributions from the 5σ level. The effectively available excitation energy in front of the adlayer is lowered by 0.5 eV. Extensive data on the variation of the intensities from the adsorbate valence levels with angle of incidence as well as of emission are presented and are analyzed in terms of an empirical model.     

Surface molecules and chemisorption: I. Adatom density of states

A useful picture of chemisorption on metal surfaces is one in which a localized molecule is formed between the adatom and its nearest neighbor substrate atoms. The interaction responsible for the molecule formation is treated as the coupling between the adsorbate state and a group orbital formed from a linear combination of atomic orbitals on the substrate atoms. Within the surface molecule picture, level width and level shift functions, given by Newns modification of the Anderson theory, have been calculated and the resulting adatom density of states function has been obtained. This has been done for model systems in which the substrate is either a free electron metal or a tightbinding p-band metal and the adsorbate is s or p like. The results show how it is possible to simultaneously have narrow virtual levels due to chemisorption (～ 1 eV) which previously implied weak interactions and also high binding energies (? 3 eV) as are observed experimentally.     

Laser induced charge transfer from Ni to CO adsorbed on (111) and (110) surfaces

Ni(110) and (111) surfaces covered with up to one monolayer of CO were irradiated with the light of a dye laser in the photon energy range 2.0 to 3.4 eV. Two-photon photoemission was observed when the laser light was focussed. Upon defocussing a signal was measured which did not depend on the potential of the sample and showed a linear intensity dependence. It is caused by electrons transferred from the Ni substrate into adsorbate states. The signal vanishes for photon energies below 2 eV. This shows that the adsorbate state lies at most 2 eV above the fermi level. The lifetime τ of the electrons in the adsorbate states is estimated to be 10^?10 < τ < 10^?7 s. No fluorescence in the photon energy range above 1 eV could be detected.     

Photostimulated desorption of metal adatoms: potassium on graphite

Photodesorption is observed of single K atoms from a graphite surface covered with less than 1 monolayer of potassium. The desorption cross section has a threshold at ħω ≈ 3 eV and a maximum at ħω_max ≈ 4.9 eV. Polarization measurements indicate a substrate-mediated mechanism. The coverage dependence suggests that only the ionic 2D, K-phase is photoactive. The proposed mechanism includes attachment of hot electrons, photoexcited in the bulk, to the K 4s adsorbate resonance of energy E_res. The band structure of graphite causes a narrow energy distribution of hot electrons, which yields ħω_max ≈ 2E_res.     

Adsorption and reaction of CO2 and CO2/O CO-adsorption on Ni(110): Angle resolved photoemission (ARUPS) and electron energy loss (HREELS) studies

Molecular adsorption is observed on a Ni(110) surface at 80 K. The relative binding energies of the valence ion states as determined by ARUPS are consistent with those in the gas as well as in the condensed phase, and indicate that the electronic structure of the adsorbed molecule is only slightly distorted upon adsorption at this temperature. The adsorbate spectra show E versus k_∥ dispersions indicating some long-range order in the adsorbate. The variations in relative ionisation probabilities of the ion states as a function of electron emission angle suggest that the molecular axis is oriented parallel to the surface within ± 20°. Upon heating the adsorbate to above 100 K. (i.e. 140 K) the spectrum changes. A new species causing an increase in work function by 1 eV can be identified. Comparison with calculations suggests that it is an anionic bent CO; molecule. Electron energy loss studies on this intermediate species support the proposed bent CO₂ geometry and favour a coordination site with C_2v symmetry. The bent CO₂ moiety is stable up to 230 K. Further heating to room temperature leads to dissociation of the bent CO₂ molecule into adsorbed CO and O. The CO molecule is oriented with its axis perpendicular to the surface. The bent CO₂ species appears to be a precursor to dissociation. Results on CO₂ adsorption on an oxygen precovered surface show that CO₂ interacts with oxygen at 85 K. Upon heating the co-adsorbate to near room temperature a reaction product is formed the nature of which cannot yet be clearly identified.     

Imaging and tunneling spectroscopy of individual iron adsorbates at room temperature

We have imaged for the first time individual atoms and small clusters of metal species on a metal substrate at room temperature by means of a scanning tunneling microscope (STM) operated under ultrahigh vacuum conditions. The system we have studied is Fe on W(110), for which a carbon-induced (15×3)-reconstruction of the W(110) substrate has been found to prevent surface diffusion of Fe atoms at 300 K. Upon positioning the STM-tip above individual Fe adsorbates, local tunneling spectra could be obtained. A pronounced empty-state peak at 0.5 eV above the Fermi level has been found, characteristic for individual Fe adsorbates. This peak can serve as a fingerprint for the identification of Fe adsorbate species.     

Ion survival probabilities for 3 keV Ar+ scattering from La,Yb, and chemisorbed H2, O2, and H2O on La surfaces

TOF spectra of scattered primary and surface recoiled neutrals and ions for 3 keV Ar⁺ bombardment of clean La and Yb and H₂, O₂, and H₂O saturated La surfaces are presented. The spectra are analyzed in terms of single (SS) and multiple (MS) scattering of the primary ions and surface recoiling (SR) of adsorbate atoms. Measurement of spectra of neutrals + ions and neutrals alone allows determination of scattered ion fractions Y. The Y values for the SS event are high for clean La (37%) and lower for adsorbate covered La (32% for H₂, 13% for O₂, and 8% for H₂O); Yb exhibits a similar behavior, i.e. 16% for clean Yb and 5% for O₂ + H₂O covered Yb. Photon emission accompanying the scattering collision has been observed from clean La and Yb and adsorbate covered La. A preferential inelastic energy loss of 15 ± 3 eV for the SS event has been observed for scattered neutrals as opposed to ions for La and H₂ saturated La at 135°. These results are interpreted within the models for Auger and resonant electronic charge exchange transitions during approach or departure of an ion with a surface and the electron promotions occuring during close atomic encounters where the electron shells are interpenetrating.     

Unoccupied electronic states on Ni(100) induced by A c(2 × 2) oxygen overlayer

Bremsstrahlung isochromat spectra at hω₀ = 9.7 eV for electrons normally incident on a clean Ni(100) surface are compared to emission from Ni(100) with an ordered c(2 × 2) oxygen overlayer. We observe strong emission due to adsorbate induced antibonding electronic states near E_F and a simultaneous attenuation of previously identified direct bulk interband transitions. The results are in accord with theoretical predictions.     

Imaging and tunneling spectroscopy of individual iron adsorbates at room temperature

We have imaged for the first time individual atoms and small clusters of metal species on a metal substrate at room temperature by means of a scanning tunneling microscope (STM) operated under ultrahigh vacuum conditions. The system we have studied is Fe on W(110), for which a carbon-induced (15×3)-reconstruction of the W(110) substrate has been found to prevent surface diffusion of Fe atoms at 300 K. Upon positioning the STM-tip above individual Fe adsorbates, local tunneling spectra could be obtained. A pronounced empty-state peak at 0.5 eV above the Fermi level has been found, characteristic for individual Fe adsorbates. This peak can serve as a fingerprint for the identification of Fe adsorbate species.     

Comparison of the electron energy loss spectrum of erbium metal with ErO2andErH2

Electron energy loss spectra of metallic erbium, Er under different exposures of oxygen at room temperature, and Er deposited in an atmosphere of H₂ are presented in both N(E) and $\text{dN}\text{dE}$ form for primary energies in the range 100–1000 eV. Resonant excitations associated with the 5p and 4d levels in Er show little environmental dependence, and are largely intraatomic in character. In contrast the main plasmon peak shifts to higher energy on exposure to oxygen or hydrogen, and the spectrum of one electron excitations at low energies alters with a decrease in metal losses around 3.5 eV accompanied by a build up of valence band transitions at 8–9 eV. There is no evidence of a stable chemisorption phase under oxygen exposure, but the results are consistent with rapid oxygen incorporation into subsurface layers and oxide formation.     

Molecular cluster theory for chemisorption of first row atoms on nickel (100) surfaces

Self-consistent Hartree-Fock-Slater molecular cluster models for the chemisorption of first row atoms on Ni(100) surfaces are presented. Energy levels and ground state charge distributions for XNi_S clusters with the adatom X = H, C, N, O located in C_{4 V} symmetry at a fixed height of h = 2.0 au above the surface are given. The variation of properties with h was studied in detail for the case of oxygen. Theoretical results compare rather well with experimental photoelectron and energy loss data. Local-densities-of-states diagrams are used to clarify the interaction between adsorbate levels and metal conduction bands.     

Electron energy loss spectroscopy study of the initial stage of lanthanum oxidation

The electron energy loss spectra (EELS) of a pure metallic lanthanum surface and variations in these spectra at the initial stages of surface oxidation were studied. The measurements were performed at primary-electron beam energies E _p from 200 to 1000 eV. A very pronounced peak at a loss energy of about 7.5 eV arises due to transitions from the La4d electronic states of the valence band into the empty La4f electronic states of the conduction band at 5.0–5.5 eV above the Fermi level. Marked changes are observed in the EELS during the oxidation of lanthanum: the peak at an energy of 7.5 eV disappears, and the peak at 13.5 eV corresponding to bulk collective energy loss in lanthanum oxide becomes more pronounced. The results obtained are discussed in terms of the electronic structure of lanthanum and lanthanum oxide.     

The kinetic MC modelling of reversible pattern formation in initial stages of thin metallic film growth on crystalline substrates

The results of kinetic MC simulations of the reversible pattern formation during the adsorption of mobile metal atoms on crystalline substrates are discussed. Pattern formation, simulated for submonolayer metal coverage, is characterized in terms of the joint correlation functions for a spatial distribution of adsorbed atoms. A wide range of situations, from the almost irreversible to strongly reversible regimes, is simulated. We demonstrate that the patterns obtained are defined by a key dimensionless parameter: the ratio of the mutual attraction energy between atoms to the substrate temperature. Our ab initio calculations for the nearest Ag-Ag adsorbate atom interaction on an MgO substrate give an attraction energy as large as 1.6 eV, close to that in a free molecule. This is in contrast to the small Ag adhesion and migration energies (0.23 and 0.05 eV, respectively) on a defect-free MgO substrate.     

Mass spectrometry study of the kinetics of CdTe molecular-beam epitaxy: Part I. Cd, Te2, and CdTe

Surface processes in CdTe molecular-beam epitaxy were studied using in situ mass spectrometry. Modulated molecular Cd and Te₂ beams were used for measuring kinetic parameters. The experiments were performed at crystal temperatures of 600–730 K. The results were processed within a model in which condensation and evaporation occur through adsorption and desorption stages. The desorption rate was 2–10 s^?1 for Te₂ and more than 30 s^?1 for Cd. The CdTe evaporation activation energy and desorption energies were determined as E _ev = 1.1 eV, E _d (Cd) = 1.0 eV, and E _d (Te) = 0.6 eV. The adsorbate coverage was estimated as n(Cd) < 0.01 and n(Te) = 0.1–1 Te.     

Spinpolarisation und Winkelverteilung der Elektronen nach Anregung verschiedener Zustände des Hg-Atoms

At energies above ～ 50 eV, electrons scattered inelastically from mercury atoms show a similarity to elastically scattered electrons in both spin polarization and angular distribution. This similarity vanishes at primary energies below ～ 30 eV for the 6p′³ P ₁-channel (11.0 eV energy loss) and below～ 25 eV for the 6¹ P ₁-channel (6.7 eV energy loss).