Oxidation of the hydrogenated diamond (100) surface

The surface composition and structure of natural diamond (100) surfaces subsequently oxidized with activated oxygen at T_sub≤35°C were investigated with high-resolution electron energy loss spectroscopy (HREELS), Auger electron spectroscopy, electron loss spectroscopy (ELS) and low-energy electron diffraction (LEED). Complete surface oxidation (oxygen coverage θ=1 ML) required doses of hundreds of kilolangmuirs of O₂. HREELS vibrational spectra permitted identification of the specific surface oxygen species, and also provided information about the diamond surface states. Most surface sites lost their hydrogen at least once before becoming oxidized. The oxygen coverage θ increased quickly at first, and then more slowly as saturation was approached; different mechanisms or sites may have accounted for the decreased rate. The relative distribution of oxygen species varied with the oxidation conditions. Ether, carbonyl and hydroxyl groups appeared during the initial stages of oxidation, but the hydroxyl groups disappeared at higher coverages. Bridge-bonded ether groups dominated at saturation coverage, although smaller amounts of carbonyl and hydroxyl were still observed. The carbonyl and C---H stretch frequencies increased with oxygen dose due to formation of higher oxidation states and/or hydrogen bonding between adjacent groups. ELS revealed only a low concentration of C=C dimers on the oxidized surfaces, and no evidence of graphitization.

Surfaces generated by oxygen addition and then desorption were more reactive than surfaces generated by hydrogen desorption. Oxidized surfaces that were heated in vacuum and then rehydrogenated did not recover the sharp LEED patterns and HREELS spectra of the original plasma-smoothed surface. This effect was presumably due to surface roughening caused by oxygen desorption as CO and CO₂, and creation of reactive high-energy sites that quickly bonded to available background gases and prevented large areas of organized surface reconstruction.     

TPD, HREELS and UPS study of the adsorption and reaction of methyl nitrite (CH3ONO) on Pt(111)

The adsorption and reaction of methyl nitrite (CH₃ONO, CD₃ONO) on Pt(111) was studied using HREELS, UPS, TPD, AES, and LEED. Adsorption of methyl nitrite on Pt(111) at 105 K forms a chemisorbed monolayer with a coverage of 0.25 ML, a physisorbed second layer with the same coverage that desorbs at 134 K, and a condensed multilayer that desorbs at 117 K. The Pt(111) surface is very reactive towards chemisorbed methyl nitrite; adsorption in the monolayer is completely irreversible. CH₃ONO dissociates to form NO and an intermediate which subsequently decomposes to yield CO and H₂ at low coverages and methanol for CH₃ONO coverages above one-half monolayer. We propose that a methoxy intermediate is formed. At least some C–O bond breaking occurs during decomposition to leave carbon on the surface after TPD. UPS and HREELS show that some methyl nitrite decomposition occurs below 110 K and all of the methyl nitrite in the monolayer is decomposed by 165 K. Intermediates from methyl nitrite decomposition are also relatively unstable on the Pt(111) surface since coadsorbed NO, CO and H are formed below 225 K.     

Structural effects on water formation from coadsorbed H + O on Rh(100)

The effect of adsorbate coverage, adsorption sequence and temperature on the structure, composition and reactivity of coadsorbed layers, produced by dissociative adsorption of O₂ and H₂ at 200 K on a Rh(100) surface, has been studied by combined TPD, XPS and LEED measurements. The emphasis is on the impact of the structure and composition of the mixed O + H layers on the synthesis of hydroxyl and water as a result of the O + H surface reaction. The difference in the O 1s binding energies of adsorbed O (529.9 eV) and OH species (530.8 eV) was used as a fingerprint to monitor the formation of the OH species. The H₂O TPD spectra show substantial variations of the desorption temperature range and the amount of water evolved with coadsorbate coverage and structure: from 270 to 350 K and from 0 to 0.08 ML, respectively. It has been found that dense O + H adlayers, where the O coverage is in the range 0.25-0.4 ML, favor the formation of stable OH species. The maximum amount of stable hydroxyl OH species ( 0.16 ML) can be produced by heating of these dense adlayers to 260 K. This results in reordering of the adspecies to form a new O + OH − (2 × 6) structure, where hydroxyls react readily to evolve 0.08 ML of water in a sharp desorption peak at 280 K. The effect of the adlayer density and restructuring on the production of OH and H₂O is discussed.     

Oxidation of heated diamond C(100):H surfaces

This paper extends a previous study (Pehrsson and Mercer, submitted to Surf. Sci.) on unheated, hydrogenated, natural diamond (100) surfaces oxidized with thermally activated oxygen (O^*₂). In this paper, the oxidation is performed at substrate temperatures from T_sub=24 to 670°C. The diamond surface composition and structure were then investigated with high resolution electron energy loss spectroscopy (HREELS), Auger electron spectroscopy (AES), electron loss spectroscopy (ELS) and low energy electron diffraction (LEED).

The oxygen coverage (θ) increased in two stages, as it did during oxidation at T<80°C. However, there are fundamental differences between the oxidation of nominally unheated and heated diamond surfaces. This difference is attributed to simultaneous adsorption and rapid desorption of oxygen species at higher temperatures; the desorption step is much slower without heating. The initial oxidation rates were similar regardless of the substrate temperatures, but the peak coverage (θ) was lower at higher temperatures. For example, θ plateaued at 0.4±0.1 ML at 600°C. The lower saturation coverage is again attributed to oxygen desorption during oxidation. Consistent results were obtained on fully oxidized surfaces, which when heated in vacuum to T_sub=600°C, lost 60% of their adsorbed oxygen. ELS revealed few C=C dimers on the oxidized surfaces, and more graphitization than on unheated surfaces. Oxidation at elevated temperatures also increased the carbonyl to ether ratio, reflecting etching-induced changes in the types of surface sites. The carbonyl and C–H stretch frequencies increased with oxygen dose due to formation of higher oxidation states and/or hydrogen bonding between adjacent groups. The oxygen types did not interconvert when the oxidized surfaces were heated in vacuum. Oxygen desorption generated a much more reactive surface than heating-induced dehydrogenation of the smooth, hydrogenated surface.     

A molecular beam study of the adsorption dynamics of CO on Ru(0001), Cu(111) and a pseudomorphic Cu monolayer on Ru(0001)

We have investigated the sticking coefficient of CO on Ru(0001), a pseudomorphic Cu monolayer on Ru(0001), and a fully relaxed Cu(111) multilayer as function of kinetic energy, surface coverage, and surface temperature. At a low kinetic energy of 0.09 eV, the initial sticking coefficients, S₀, on these surfaces are determined to be 0.92, 0.96 and 0.87, respectively. In all cases, a decrease of S₀ with increasing beam energy was observed, yielding values of 0.58, 0.14 and 0.07, respectively, at a kinetic energy of 2.0 eV. For all three surfaces the coverage dependent sticking coefficients, S(Θ), display very characteristic behavior at low kinetic energies: S(Θ) remains more or less constant up to coverages close to saturation, indicative of precursor adsorption kinetics. However, characteristic minima at intermediate coverages are observed, which are correlated to the formation of well ordered adsorbate phases. For high kinetic energies we observe a transition towards a linear decrease of S(Θ) for Ru(0001). In contrast, for the pseudomorphic Cu monolayer and for Cu(111) we find an increase in the sticking coefficients at low coverages, followed by a decrease close to saturation. This behavior is attributed to adsorbate assisted sticking, that is, to a higher sticking coefficient on adsorbate covered regions than on the bare surface. The comparison between the pseudomorphic monolayer and Cu(111) reveals that the CO bond strength to the former is larger by 40%. The initial sticking coefficients for both surfaces are very similar at low kinetic energies; at high kinetic energies, S₀ for the pseudomorphic Cu monolayer is, however, larger by a factor of two.     

Hydrogen adsorption on Mo1−xRex(110) (x=0–0.25) surfaces

The effects of adsorbed H on the Mo_1−xRe_x(110), x=0, 0.05, 0.15, and 0.25, surfaces have been investigated using low-energy electron diffraction (LEED) and high-resolution electron energy loss spectroscopy (HREELS). For the x=0.15 alloy only, a c(2×2) LEED pattern is observed at a coverage Θ0.25 ML. A (2×2) pattern is observed for H coverages around Θ0.5 ML from surfaces with x=0, 0.05, and 0.15. Both c(2×2) and (2×2) patterns are attributed to reconstruction of the substrate. At higher coverages, a (1×1) pattern is observed. For the alloy surface with x=0.25, only a (1×1) pattern is obtained for all H coverages. Two H vibrations are observed in HREELS spectra for all Re concentrations, which shift to higher energies at intermediate coverages. Both peaks exhibit an isotopic shift, confirming their assignment to hydrogen. For Re concentrations of x=0.15 and higher, a third HREELS peak appears at 50 meV as H (D) coverage approaches saturation. This peak does not shift in energy with isotopic substitution, yet cannot be explained by contamination. The intrinsic width of the loss peaks depends on the Re concentration in the surface region and becomes broader with increasing x. This broadening can be attributed to surface inhomogeneity, but may also reflect increased delocalization of the adsorbed hydrogen atom.     

Interaction of oxygen with the Pt(1 1 1) surface in wide conditions range. A DFT-based thermodynamical simulation

We present the results of ab initio calculations of oxygen atomic adsorption in a wide range of coverage on Pt(1 1 1). At θ = 0.25 ML, the O adsorption at fcc hollow site is clearly favoured over the hcp site. At θ = 0.5 ML, the O adsorption energy decreases but the same site is favoured. When experimental or theoretical previously reported data are available, the calculated adsorption energies and site preferences are in good agreement. Among the various configurations and coverages investigated in the present work, no adsorption is stable beyond θ = 0.5 ML, except by occupation of a subsurface tetrahedral site. In that case, a total O coverage of 0.75 ML could be achieved, which is only slightly less stable than the θ = 0.5 ML configuration.

The use of thermodynamics permitted to explore the temperature–pressure stability domain corresponding to 0.25 ML, 0.5 ML and 0.75 ML. From this, we conclude that subsurface O species could be stable at temperatures lower than 700 K, with O₂ pressures of 1 bar or less.     

Enhanced transient reactivity of an O-sputtered Au(1 1 1) surface

The interaction of SO₂ with oxygen-sputtered Au(1 1 1) (θ_oxygen  0.35 ML) was studied by monitoring the oxygen and sulfur coverages as a function of SO₂ exposure. The morphology of the sputtered Au is relatively smooth on a long length scale, but rough on a finer scale with islands averaging 15 nm. The rough surface is not stable to scanning with the STM. Two reaction regimes were observed: oxygen depletion followed by sulfur deposition. An enhanced, transient sulfur deposition rate is observed at the oxygen depletion point. This effect is specifically pronounced if the Au surface is continuously exposed to SO₂. The enhanced reactivity towards S deposition seems to be linked to the presence of highly reactive, under-coordinated Au atoms. Adsorbed oxygen appears to stabilize, but also to block these sites. In absence of the stabilization effect of adsorbed oxygen, i.e. at the oxygen depletion point, the enhanced reactivity decays on a timescale of a few minutes. These observations shed a new light on the catalytic reactivity of highly dispersed gold nanoparticles.     

Structure and NO reactivity of Zr-deposited Pd surfaces

The structure and NO reactivity of Zr-deposited Pd surfaces were investigated by X-ray photoelectron spectroscopy, low-energy electron diffraction, infrared reflection absorption spectroscopy, and temperature-programmed desorption. Zr on Pd(1 0 0) was oxidized to ZrO₂ by exposure to O₂ at 773 K. Heating at 823 K in a vacuum led to decomposition of ZrO₂ to Zr metal and O₂. The activation energy for ZrO₂ decomposition changed remarkably at Θ_Zr = 0.4. For Θ_Zr > 0.4, a hexagonal structure was observed for ZrO₂/Pd(1 0 0); no ordered structure was observed for Θ_Zr < 0.4. Deposited Zr had no significant effect on the adsorption and decomposition of NO on Pd(1 0 0) but resulted in a creation of new NO dissociation sites on Pd(3 1 1). Zr on Pd(3 1 1) was oxidized to ZrO_X by oxygen produced from NO dissociation. Heating at 823 K in a vacuum led to decomposition of ZrO_X to Zr metal and O₂.     

Thermal desorption of surface phosphorus on Si(100) surfaces

Thermal desorption of phosphorus on Si(100) surfaces has been investigated by varying the phosphorus coverage from zero to one monolayer (ML). The reaction path of phosphorus desorption is complicated and strongly dependent upon the phosphorus coverage. In the thermal desorption spectra, there are three apparent desorption peaks at 750, 850 and 1000°C. The entire phosphorus atoms on the surface desorb as P₂ through recombinative reactions irrespective of the desorption temperature and the coverage. In the lower coverages below 0.2 ML, the thermal desorption spectra are characterized by a single peak at 900°C which is considered to be the desorption from Si---P heterodimers. At higher coverages exceeding 0.2 ML, it is considered that three desorption schemes from P---P, Si---P dimers and defects coexist in the reaction stage.     

Work function changes and surface chemistry of oxygen, hydrogen, and carbon on indium tin oxide

The surface chemistry of indium tin oxide (ITO) has been investigated with Auger electron spectroscopy (AES) and high resolution electron energy loss spectroscopy (HREELS). A vibrating Kelvin probe (KP) with a graphite reference was used to monitor the absolute work function (Φ) of ITO as a function of chemical modification. The ITO was exposed in situ to molecular hydrogen (H₂), hot-filament-activated oxygen (O₂^*), and hot-filament-activated deuterium (D₂^*). The initial Φ of ITO was determined to be 5.2 eV, and surface chemical changes had strong effects on this value, as seen by KP. Exposure of clean ITO to O₂^* increased Φ to 5.6 eV, but the increase was short-lived. The changes in Φ over time were correlated with the uptake of carbon impurities in ultra high vacuum (UHV), as monitored by AES.

The HREELS of ITO revealed significant hydrocarbon impurities. Chemical reduction of ITO produced a metallic surface and dehydrogenated the adsorbed hydrocarbons. Both re-oxidation of metallic ITO and oxidation of clean ITO temporarily removed adventitious carbon from the surface, but oxidized ITO adsorbed an even larger quantity of carbon over time.     

The adsorption of CO on Ir(111) investigated with FT-IRAS

The adsorption of CO on Ir(111) has been investigated with Fourier transform infrared reflection-absorption spectroscopy, temperature programmed desorption, and low-energy electron diffraction. At sample temperatures between 90 and 350 K, only a single absorption band, above 2000 cm⁻¹, has been observed at all CO coverages. For fractional coverages above approximately 0.2, the bandwidth becomes as narrow as 5.5 cm⁻¹. The linewidth is attributed mainly to inhomogeneous broadening at low CO coverages and to the creation of electron-hole pairs at higher CO coverages. The coverage-dependent frequency shift of the IR band can be described quantitatively using an improved dipolar coupling model. The contribution of the dipole shift and the chemical shift to the total frequency shift were separated using isotopic mixtures of CO. The chemical shift is positive with a constant value of approximately 12 cm⁻¹ for all coverages, whereas the dipole shift increases with coverage up to a value of 36 cm⁻¹ at a coverage of 0.5 ML.     

Adsorption of oxygen and carbon dioxide on cesium-reconstructed Ag(1 1 0) surface

The adsorption of oxygen and carbon dioxide on cesium-reconstructed Ag(1 1 0) surface has been studied with scanning tunneling microscopy (STM) and temperature programmed desorption (TPD). At 0.1 ML Cs coverage the whole surface exhibits a mixture of (1 × 2) and (1 × 3) reconstructed structures, indicating that Cs atoms exert a cooperative effect on the surface structures. Real-time STM observation shows that silver atoms on the Cs-covered surface are highly mobile on the nanometer scale at 300 K. The Cs-reconstructed Ag(1 1 0) surface alters the structure formed by dissociative adsorption of oxygen from p(2 × 1) or c(6 × 2) to a p(3 × 5) structure which incorporates 1/3 ML Ag atoms, resulting in the formation of nanometer-sized (10–20 nm) islands. The Cs-induced reconstruction facilitates the adsorption of CO₂, which does not adsorb on unreconstructed, clean Ag(1 1 0). CO₂ adsorption leads to the formation of locally ordered (2 × 1) structures and linear (2 × 2) structures distributed inhomogeneously on the surface. Adsorbed CO₂ desorbs from the Cs-covered surface without accompanied O₂ desorption, ruling out carbonate as an intermediate. As a possible alternative, an oxalate-type surface complex [OOC–COO] is suggested, supported by the occurrence of extensive isotope exchange between oxygen atoms among CO₂(a). Direct interaction between CO₂ and Cs may become significant at higher Cs coverage (>0.3 ML).     

Optical second-harmonic investigations of the isothermal desorption of SiO from the Si(100) and Si(111) surfaces

The isothermal desorption of SiO from the Si(100) and Si(111) surfaces was investigated by means of optical second-harmonic generation (SHG). Due to the high adsorbate sensitivity of this method, desorption rates could be measured over a wide range from 10⁻¹ to 10⁻⁶ ML s⁻¹. From their temperature dependence between 780 and 1000 K, activation energies of E_A=3.4±0.2 eV and E_A=4.0±0.3 eV and pre-exponential factors of ν₀=10^16±1 s⁻¹ and ν₀=10^20±1 s⁻¹ for SiO desorption were obtained for Si(100) and Si(111), respectively. In the case of the Si(100) surface, a pronounced decrease of the first-order rate constants was observed upon increasing the initial coverage from 0.02 to 0.6 ML. The results are interpreted in terms of coverage-dependent oxygen-binding configurations, which influence the stability of the oxide layer.     

Effect of surface orientation and sulfur coverage on the oxidation of carbon on Ni surfaces

The reaction between adsorbed oxygen and segregated carbon on a cylindrical nickel single-crystal has been examined with Auger electron spectroscopy (AES) and temperature programmed desorption (TPD), for a range of surface orientation, oxygen exposure, and sulfur coverage. It was found that for small oxygen exposures, surface carbon and surface oxygen react during TPD to form a CO desorption peak, labeled β₁. The β₁ CO peak temperature and peak shape vary with orientation. At higher oxygen coverages, the CO desorption peak split into low-temperature and high-temperature peaks. The behavior of the β₁ CO desorption peak for large oxygen exposures is consistent with a model of the carbon-oxygen recombination reaction in which the morphologies of the initial carbon and oxygen phases change during oxygen exposure as a result of repulsive lateral interactions. High oxygen exposures result in the formation of large regions of contact between the two phases; this is believed to produce the low-temperature β₁ CO desorption peak. Small segregated-sulfur coverages, and low oxygen exposures, caused the β₁ CO peak to shift to lower temperatures for all orientations. Sulfur is believed to cause more frequent contact between carbon and oxygen for small oxygen exposures because it compresses the adsorbed oxygen and segregated carbon into the sulfur-free areas of the surface. Large coverages of segregated sulfur inhibited carbon segregation on some, and oxygen adsorption on most, orientations. The absence of reactant species explains the disappearance of the β₁ CO peak during TPD from orientations which had a high sulfur coverage.     

Formation of Mo and MoSx nanoparticles on Au(1 1 1) from Mo(CO)6 and S2 precursors: electronic and chemical properties

Mo(CO)₆ can be useful as a precursor for the preparation of Mo and MoS_x nanoparticles on a Au(1 1 1) substrate. On this surface the carbonyl adsorbs intact at 100 K and desorbs at temperatures lower than 300 K. Under these conditions, the dissociation of the Mo(CO)₆ molecule is negligible and a desorption channel clearly dominates. An efficient dissociation channel was found after dosing Mo(CO)₆ at high temperatures (>400 K). The decomposition of Mo(CO)₆ yields the small coverages of pure Mo that are necessary for the formation of Mo nanoclusters on the Au(1 1 1) substrate. At large coverages of Mo (>0.15 ML), the dissociation of Mo(CO)₆ produces also C and O adatoms. Mo nanoclusters bonded to Au(1 1 1) exhibit a surprising low reactivity towards CO. Mo/Au(1 1 1) surfaces with Mo coverages below 0.1 ML adsorb the CO molecule weakly (desorption temperature<400 K) and do not induce C–O bond cleavage. These systems, however, are able to induce the dissociation of thiophene at temperatures below 300 K and react with sulfur probably to form MoS_x nanoparticles. The formed MoS_x species are more reactive towards thiophene than extended MoS₂(0 0 0 2) surfaces, MoS_x films or MoS_x/Al₂O₃ catalysts. This could be a consequence of special adsorption sites and/or distinctive electronic properties that favor bonding interactions with sulfur-containing molecules.     

Surface diffusion of dysprosium on the W(1 1 1) facet

Diffusion of dysprosium on the (1 1 1) facet of a tungsten micromonocrystal was investigated by means of spectral analysis of field emission current fluctuations. The experimental spectral density functions of the current fluctuations were analysed by using Gesley and Swanson’s theoretical spectral density function, which enables to determine the surface diffusion coefficient D for dysprosium. Derived from the temperature dependence of D, the diffusion activation energy E is presented for some Dy coverages θ_(1 1 1). In the temperature range 400–600 K, the E first drops from 1.25 eV per atom at θ₍₁₁₁₎≈0.25 ML to 0.48 eV per atom at θ₍₁₁₁₎≈1 ML (corresponding to the minimum of the work function of the system), then increases to 1.03 eV per atom at θ₍₁₁₁₎≈1.3 ML. The results are discussed from the aspects of the substrate structure and interaction in the adsorbed layer.     

Oxygen adsorption and oxidation reactions on Au(2 1 1) surfaces: Exposures using O2 at high pressures and ozone (O3) in UHV

Nanosized gold particles supported on reducible metal oxides have been reported to show high catalytic activity toward CO oxidation at low temperature. This has generated great scientific and technological interest, and there have been many proposals to explain this unusual activity. One intriguing explanation that can be tested is that of Nørskov and coworkers [Catal. Lett. 64 (2000) 101] who suggested that the “unusually large catalytic activity of highly-dispersed Au particles may in part be due to high step densities on the small particles and/or strain effects due to the mismatch at the Au-support interface”. In particular, their calculations indicated that the Au(2 1 1) stepped surface would be much more reactive towards O₂ dissociative adsorption and CO adsorption than the Au(1 1 1) surface. We have now studied the adsorption of O₂ and O₃ (ozone) on an Au(2 1 1) stepped surface. We find that molecular oxygen (O₂) was not activated to dissociate and produce oxygen adatoms on the stepped Au(2 1 1) surface even under high-pressure (700 Torr) conditions with the sample at 300-450 K. Step sites do bind oxygen adatoms more tightly than do terrace sites, and this was probed by using temperature programmed desorption (TPD) of O₂ following ozone (O₃) exposures to produce oxygen adatoms up to a saturation coverage of θ_O = 0.90 ML. In the low-coverage regime (θ_O ? 0.15 ML), the O₂ TPD peak at 540 K, which does not shift with coverage, is attributed to oxygen adatoms that are bound at the steps on the Au(2 1 1) surface. At higher coverages, an additional lower temperature desorption peak that shifts from 515 to 530 K at saturation coverage is attributed to oxygen adsorbed on the (1 1 1) terrace sites of the Au(2 1 1) surface. Although the desorption kinetics are likely to be quite complex, a simple Redhead analysis gives an estimate of the desorption activation energy, E_d, for the step-adsorbed oxygen of 34 kcal/mol and that for oxygen at the terraces near saturation coverage of 33 kcal/mol, values that are similar to others reported on Au surfaces. Low Energy Electron Diffraction (LEED) indicates an oxygen-induced step doubling on the Au(2 1 1) surface at low-coverages (θ_O = 0.08-0.17 ML) and extensive disruption of the 2D ordering at the surface for saturation coverages of oxygen (θ_O ? 0.9 ML). Overall, our results indicate that unstrained step sites on Au(2 1 1) surfaces of dispersed Au nanoparticles do not account for the novel reactivity of supported Au catalysts for CO oxidation.     

Structure of the Si(011)-(16 × 2) surface and hydrogen desorption kinetics investigated using temperature-programmed desorption

D₂ temperature-programmed desorption (TPD) was used to probe the structure of the Si(011)-(16 × 2) surface. Deuterium was adsorbed at 200°C to coverages θ_D ranging up to complete saturation (approximately 1.1 ML) and the sample heated at 5°C s⁻¹. TPD spectra exhibited three second-order desorption peaks labelled β₂, β*₁ and β₁ centered at 430, 520 and 550°C. Of the proposed models for the Si(011)-(16 × 2) reconstruction, the present TPD results as a function of θ_D provide support for the adatom/dimer model with the β₂ peak assigned to D₂ desorption from the dihydride phase, while the β*₁ and β₁ peaks arise from adatom and surface-atom monohydride phases.     

Transmission of low-energy (< 10 eV) O ions through Au films on TiO2(110)

In an attempt to identify the fundamental processes that influence ion transport through metallic surface layers, we have studied the transmission of O⁺ ions through discontinuous Au films adsorbed on TiO₂(110). A low energy (< 10 eV) O⁺ ion beam is generated via electron stimulated desorption when an Au-dosed TiO₂(110) substrate is bombarded with a focused 250 eV electron beam. Low energy ion scattering data indicate that Au evaporated under ultrahigh vacuum conditions at 300 K forms three-dimensional clusters on TiO₂(110). As the Au coverage increases, the formation of Au clusters on TiO₂(110) blocks a fraction of the TiO₂ surface and the O⁺ yield is attenuated. However, for high coverages (≥30% Au covered substrate) the O⁺ signal decreases at a faster rate than the TiO₂ open area fraction. We attribute the attenuation of the O⁺ yield for high Au coverages mainly to blocking of O⁺ by Au clusters, to deflection of trajectories by the image force between ions and Au clusters, and to charge transfer between desorbing O⁺ and neighboring Au clusters.