Electronic properties of clean (001) surfaces of Ir and Pt

We present a theoretical investigation of the electronic structure of the ideal (001) surface of Ir and Pt. Surface band structures and local densities of states have been determined using a parametrized linear combinatiion of atomic orbitals for a film of fourteen (001) atomic planes. Various surfaces states and resonances arise in correspondence of the gaps of the projected bulk band structure. Our results explain the experimetnal data, obtained in field ion emission and conventional photoemission experiments, showing a surface sensitive structure in the proximity of the Fermi energy.     

Preparation and chemisorptive properties of the clean normal and reconstructed surfaces of Ir(100) — role of multiplets

The preparation and properties of the clean normal (1 × 1)Ir(100) and the reconstructed (1 × 5)Ir(100) metal surfaces are reported. Photoemission studies of the chemisorptive bonding of carbon monoxide, of hydrogen and of oxygen on the Ir(100) surface are discussed. The possible occurrence of multiplets in the photoemission spctra for chemisorbed oxygen on cesium; Ni(111) and Ir(100) is proposed and evidence for their importance is presented.     

Field ion microscope observations of surface reconstructions on Pt(100) and Ir(100)

The reconstruction of the Pt(100) and Ir(100) plane has been studied by field ion microscopy. Small clusters of atoms produced by low-temperature field evaporation transform to new structures at temperatures above 270 K for Pt and 470 K for Ir. The atomic structure of reconstructed images is not resolved, but the shapes of the clusters suggest reconstructions consistent with current models based on low energy electron diffraction studies. Field evaporation of the reconstructed surfaces indicates that the restructuring extends to the second layer of atoms.     

Oxygen adsorption on clean Mo (100) surfaces

Oxygen adsorption on clean Mo (100) surfaces has been studied by LEED, AES, work function changes and energy loss spectroscopy. At room temperature, the oxygen uptake as determined by AES is linear up to one third of the saturation value. Data obtained with CO adsorption have been used to determine the oxygen coverage. With increasing oxygen exposure LEED shows three stages: a c (2 × 2) phase growing simultaneously with a (6 × 2) structure, a stage with (110) microfacets covered by two-dimensional structures and finally a p (3×1) structure together with a p (1×1) structure, probably due to an oxide phase. Even in the low temperature range (370–500 K) remarkable effects are observed: adsorption at 370 K produces a disordered c (4×4) structure which is followed by a (√5 × √5)?R 26° 33 structure. The same occurs when the inital c (2 × 2) structure formed at 295 K is heated above 370 K. Measurements of the work function indicate a minimum at the end of the c (2×2) structure, then a rapid increase and at saturation a value of about 1.5 V above that of the clean surface. Energy loss spectroscopy measurements point to an increase of the surface plasmon energy during the faceting stage. New transitions are observed which are due to new electronic levels induced by the adsorption. They are comparable with photoemission results on W and Mo.     

Chemisorptive bonding and reaction of nitric oxide on Ir(100) and Ir(111) surfaces

Chemisorption of nitric oxide on single crystal Ir(111) and Ir(100)?(5 × 1) has been studied by UV-photoelectron spectroscopy, thermal desorption and low energy electron diffraction. At 300 K, partially dissociative adsorption is observed on both surfaces, confirming the borderline location of Ir in the Periodic Table with respect to molecular versus dissociative adsorption. Three different molecular chemisorption phases are distinguished in the UPS spectra through distinctly different 1π-level energies. A skewed orientation associated with a possible rehybridization and bending of the nitrosyl-metal bound for chemisorption on the Ir(111) surface is inferred both from a splitting of the 1π level and from observation of relative intensity variations in photoemission using a polarized photon source.     

Photoemission studies of clean and oxygen-covered Pt 6(111) × (100)

Employing the enhanced sensitivity obtained by using synchrotron radiation near the Cooper minimum for the 5d valence electrons, we have located the oxygen 2p and 2s levels for oxygen chemisorbed on a Pt 6(111) × (100) crystal. We find the oxygen 2p level located ?6 eV with a FWHM of 3 eV and the 2s at ?21.6 eV. A factor of four difference in saturation coverage is measured between temperatures of 300 and 120 K, but the position and width of the 2p level is independent of temperature. We observe also the 1b₁ orbital of weakly adsorbed H₂O molecules, which has pure O 2p parentage; from the intensity of this orbital, we are able to suggest why it is difficult to observe the oxygen 2p signal at low photon energies. In addition, we note a strong preferential attenuation in the Pt states near E_f for the adsorbed H₂O in spite of the weak nature of the bond.     

Electronic properties of clean and oxygen exposed GaAs (100) surfaces

Both Photoemission Yield Spectroscopy (PYS) and Auger Electron Spectroscopy (AES) have been used in the study of the electronic properties of the clean GaAs(100) surface prepared by IBA procedure and subsequently exposed to oxygen. For the clean GaAs(100)c(8 × 2) surface, the values of the work function and the absolute band bending were 4.20 ± 0.02 eV and −0.23 ± 0.06 eV, respectively, which confirms the pinning of the Fermi level E_F, and two filled electronic surface state bands localized in the band gap below the Fermi level were observed. After exposition of this surface to 10³ L of oxygen, the electronic surface state band localized just below the Fermi level E_F disappeared, and the work function and the absolute band bending increased by only 0.12eV, whereas for the higher oxygen exposures of 10⁴L and 10⁵L, only small increases in the values of the work function and the absolute bending by 0.04 eV and 0.03 eV, respectively, were observed.     

Electron energy-loss spectra of clean and gas-covered Ni(100) surfaces

Electron energy-loss spectra have been measured on Ni(100) surfaces, clean and following oxygen and carbon monoxide adsorption, at primary energies of 40–300 eV. The observed peaks at 9.1, 14 and 19 eV in the clean-surface spectrum are ascribed to the bulk plasmon of the 4s electrons, the surface plasmon, and the bulk plasmon of the coupled 3d + 4s electron, respectively, and the weak but sharp peak at 33 eV is tentatively attributed to the localized many-body effect in the final state. Assignments of the loss structures on the gas-covered surfaces have been attempted.     

High coverage states of oxygen adsorbed on Pt(100) and Pt(111) surfaces

Oxygen adsorption on the Pt(100) and Pt(111) surfaces was investigated using X-ray photo-emission and thermal desorption spectroscopies. Low pressure (ca. 10^?5 Pa) oxygen dosing at near ambient crystal temperature resulted in the formation of dissociated adsorbed species at saturation coverages of nominally 0.2–0.25 monolayer on both surfaces. The combination of higher pressure (ca. 10^?3 Pa) and higher surface temperature (570 K) dosing produced a three to five times higher saturation coverage than the low pressure dosing. The effect of dosing condition on the saturation coverage appears to reconcile apparent discrepancies for the Pt(100) surface in the literature. Characterization by XPS of the higher coverage state for oxygen showed that it is in the same chemical state as the oxygen adsorbed at very low coverage. Angle-resolved XPS has shown that in all cases the oxygen appears to reside on the surface with no significant penetration of oxygen into the bulk, as would be characteristic of oxidation. However, some penetration on the surface by oxygen, such as by a place-exchange type restructuring of the first two atomic layers, cannot be entirely ruled out.     

Valence band studies of clean and oxygen exposed GaAs(100) surfaces

We found, by correlating band bending, ultraviolet photoemission spectroscopy, and partial yield spectroscopy measurements, that Fermi level pinning at midgap of n-type GaAs(110) is caused by extrinsic states. The exact nature of these states is not yet clear, but the surfaces with Fermi level pinning were strained as evidence by a smeared valence band emission. This smearing was removed by as little as one oxygen per 10⁴ to 10⁵ surface atoms. This implies that the oxygen has very long range effects in causing spontanesous but small rearrangement of the surface lattice and removing surface strains. When about 5% of a monolayer of oxygen is adsorbed, a major change in the electronic structure takes place. Again, the oxygen coverage is very small, which suggests long range effects now leading to a fairly large rearrrangement of the surface lattice. Finally, from comparing the oxygen induced emission for exposures greater than 10⁷ L O₂, with the spectra from gas photoemission measurements on molecular oxygen, we suggest that the oxygen is chemisorbed as a molecule on the (110) surface of GaAs.     

Segregation of Pt at clean surfaces of (Pt, Ni)3Al

Experimental evidence for surface segregation of Pt at (1 1 1) surfaces of ternary (Pt, Ni)₃Al alloys is presented, based upon Auger electron spectroscopy, low energy ion scattering, and angle-resolved X-ray photoelectron spectroscopy. Density functional calculations in the dilute limit confirm that Pt segregation is energetically favored.     

LEED intensities from clean and hydrogen covered Ni(100) and Pd(111) surfaces

Hydrogen adsorbs on Ni(100) and Pd(111) surfaces without the formation of additional diffraction spots in the LEED patterns. Measurements of LEED intensities revealed that adsorbed hydrogen layers cause considerable changes even in such cases where displacements of surface atoms (“reconstructive adsorption”) may be excluded. After hydrogen adsorption on Ni(100) the intensities of Bragg beams are uniformly lowered whereas the background intensity increases which is attributed to the formation of a disordered adsorbed layer. With Pd(111) adsorbed hydrogen causes a slight decrease of the background intensity and characteristic modifications of the intensity/voltage curve of the (0,0) beam, suggesting the formation of an ordered 1 × 1 structure. In the latter case energy shifts of the primary Bragg maxima were observed and are interpreted as being caused by an expansion of the layer spacing in the surface region by about 2% owing the partial dissolution of the hydrogen.     

Reactions and structures of water on clean and oxygen covered Pt(111) and Fe(100)

An atom superposition and election delocalization (ASED) technique applied to water adsorption on a small cluster model of Pt(111) shows weak and reversible chemisorption and facile and reversible hydrogen transfer to preadsorbed oxygen atoms as observed by Fisher, Sexton and Gland in EELS and UPS studies. Our theory predicts much stronger adsorption of water to Fe(100) with low barriers to dehydrogenation, in agreement with high temperature LEED-Auger results of Dwyer, Simmons, and Wei and wide temperature range XPS studies of Akimov. We predict a low barrier to transfer of hydrogen from water to adsorbed oxygen atoms, forming hydroxyl groups on the iron surface, and a fairly low barrier to the reverse reaction. On both metals we find hydroxyl groups are strongly held. Our calculations produce a trend toward greater negativity on going from adsorbed water to hydroxyl groups, and to hydroxyl dissociation products on these surfaces. We present reaction mechanisms, transition state geometries, and analysis in terms of molecular orbital theory and the total energy. It is found that the platinum is generally less reactive than iron toward water and hydroxyl species because platinum orbitals are less diffuse and the platinum s-d band lies lower, closer to adsorbate energy levels such that adsorbate-platinum antibonding orbitals are filled.     

The adsorption of acetic acid on clean and oxygen-covered Au/Pd(100) alloy surfaces

The adsorption of acetic acid is studied on clean and oxygen-covered Au/Pd(100) alloys as a function of gold content by temperature-programmed desorption and reflection–absorption infrared spectroscopy. Au/Pd(100) forms ordered alloys such that, for gold coverages above ~ 0.5 monolayers, only isolated palladium atoms surrounded by gold nearest neighbors are present. Predominantly molecular acetic acid forms on Au/Pd(100) alloy surfaces for gold coverages greater than ~ 0.56 ML, and desorbs with an activation energy of ~ 59 kJ/mol. Heating this surface also forms some η¹-acetate species which decompose to form CO and hydrogen. On alloy surfaces with palladium–palladium bridge sites, η¹-acetate species initially form, but rapidly convert into η²-species. They thermally decompose to form CO and hydrogen, with a small portion rehydrogenating to form acetic acid between 280 and 321 K depending on gold coverage. The presence of oxygen on both Pd(100) and Au/Pd(100) alloys facilitates acetate dehydrogenation so that only η²-acetate species form on these surfaces. The presence of oxygen also serves to stabilize the acetate species.     

On the nonlinear dynamics in the oxidation of CO on Pt(100) and Pt(110) surfaces: Forced oscillations

The effects of low-amplitude periodic modulation of oxygen pressure on the catalytic oxidation on Pt(100) and Pt(110) are investigated with the aid of a set of kinetic equations derived by Cox, Ertl and Imbihl. In the response of the system, subharmonic and superharmonic entrainment bands are found in addition to the fundamental entrainment band. Furthermore, quasiperiodic oscillations are obtained between the entrainment bands.     

The structure of the Pt(100) surface

The atomic arrangement in the first two layers of the clean Pt(100) surface is described from a Fourier analysis of low energy electron diffraction (LEED) intensities. The Fourier transform and sensible platinum-platinum bond lengths require that the top layer is corrugated, the corrugation “step” being approximately 0.4 Å. The structure of the first layer is partly described by a hcp rearrangement from the bulk fcc structure. The rearrangement is related to geometrical and electronic properties of the metals. Some qualitative and quantitative comments are made on the general value of Fourier methods in surface crystallography.     

Reflectometric study of surface states and oxygen adsorption on clean Si(100) and (110) surfaces

External differential reflection measurements were carried out on clean Si(100) and (110) surfaces in the photon energy range of 1.0 to 3.0 eV at 300 and 80 K. The results for Si(100) at 300 K showed two peaks in the joint density of states curve, which sharpened at 80 K. One peak at 3.0 ± 0.2 eV can be attributed to optical transitions from a filled surface states band near the top of the valence band to empty bulk conduction band levels. The other peak at 1.60 ± 0.05 eV may be attributed to transitions to an empty surface states band in the energy gap. This result favours the asymmetric dimer model for the Si(100) surface. For the (110) surface at 300 K only one peak was found at 3.0 ± 0.2 eV. At 80 K the peak height diminished by a factor of two. Oxygen adsorption in the submonolayer region on the clean Si(100) surface appeared to proceed in a similar way as on the Si(111) 7 × 7 surface. For the Si(110) surface the kinetics of the adsorption process at 80 K deviated clearly. The binding state of oxygen on this surface at 80 K appeared to be different from that on the same surface at 300 K.     

Reactions of formaldehyde and methanol on clean,carburized and oxidized Mo(100) surfaces

The reactions of formaldehyde and methanol have been studied on clean, carburized, and oxidized Mo(100) surfaces using temperature programmed reaction spectroscopy (TPRS). The thermal cracking of ethylene at 550 K and the adsorption of molecular oxygen at 1050 K were used to carburize and oxidize, respectively, the clean surface to saturation. Both the carbide and oxide surfaces showed (1×1) LEED features. Methanol decomposed to give hydrogen atoms and methoxy intermediates upon adsorption on the clean Mo(100) surface at 200 K. The methoxy intermediate was stable up to 340 K. Adsorbed carbon and oxygen suppressed the dissociation of the hydroxyl hydrogen from the alcohol and yielded a significantly different activity and selectivity compared to the very reactive clean surface. The binding energies for both formaldehyde and methanol on the three surfaces were similar, demonstrating the weak sensitivity of donor-acceptor bonds to surface modifiers. The results in this study were very similar to those previously observed for W(100) though different adlayer structures were present. This similarity suggested that the modification in surface reactivity was primarily a compositional effect.