Interactions between SO2 and NO on the surface of stepped Pt(3 3 2)

Interactions between S¹⁸O₂ and NO on the surface of stepped Pt(3 3 2) were studied using Fourier transform infra red reflection-absorption spectroscopy (FTIR-RAS) combined with thermal desorption spectroscopy (TDS). Adsorbed S¹⁸O₂ does not seem to have a preference for step sites on Pt(3 3 2). As such, the presence of S¹⁸O₂ molecules following exposures of ?1.6 L does not significantly block the subsequent adsorption of NO (?0.8 L) on these step sites. Adsorbed S¹⁸O₂ molecules undergo dissociation (S¹⁸O₂(a) → S¹⁸O(a) + ¹⁸O(a)) as the surface temperature is increased to 250 K and above, but the resultant ¹⁸O(a) further reacts with sulfur oxides (S¹⁸O₂(a) and S¹⁸O(a)) to form S¹⁸O_x (x > 2) species at ∼400 K and above. The S¹⁸O_x species desorb as S¹⁸O₂. Even though the presence of co-adsorbed S¹⁸O₂ suppresses NO dissociation and subsequent N₂ production, this effect is not significantly enhanced with increasing the exposures of S¹⁸O₂ in the range ?1.6 L; N₂ desorption is still detectable at an exposure of 1.6 L S¹⁸O₂, at which a considerable amount of S¹⁸O₂ desorption is detected.     

UPS and XPS studies of the chemisorption of O2, H2 AND H2O on reduced and stoichiometric SrTiO3(111) surfaces; The effects of illumination

About one monolayer of Ti³⁺ species is detectable at the surface of reduced SrTiO₃(111) single crystals by XPS and UPS. O₂, H₂ and H₂O have been adsorbed in the dark and the decrease on the concentration of the Ti³⁺ species has been monitored as a function of the gas exposures. Subsequent band gap illumination partially restores the Ti³⁺ initial concentration in the cases of O₂ and H₂ exposures but not in the case of H₂O. The Ti³⁺ photogeneration on the oxygen covered surface is associated with oxygen photodesorption as indicated by XPS and UPS. UPS measurements give evidence for surface hydroxylation resulting from water and hydrogen adsorption. The activity of the stoichiometric SrTiO₃(111) crystal face for O₂ and H₂ adsorption is very low when compared with the reduced SrTiO₃ samples.     

Adsorption of oxygen on a Cu{110} surface with and without the influence of A keV Ne+ beam: Stage I: Coverages up to half a monolayer

Low Energy Ion Scattering has been used to study the interaction of molecular oxygen with a Cu{110} surface. The amount of adsorbed atomic oxygen was monitored by the 4 keV Ne⁺¦O reflection signal. In the first adsorption stage (coverage less than half a monolayer) the sticking probability varied proportional to the number of empty adsorption sites: S = S₀ (1 ? $\text{}\text{?}$gq). It turned out not to be influenced by the Ne⁺ bombardment. The initial sticking probability S₀ was found to be ≈ 0.24. In this first adsorption stage the oxygen-covered surface is reconstructed according to the “missing row” model, leading to a (2 × 1) LEED pattern.     

The properties of K and coadsorbed CO + K on Ru(001): I. Adsorption,desorption, and structure

An extensive photoemission and LEED study of K and CO+K on Ru(001) has been carried out. In this paper the LEED and some XPS results together with TPD and HREELS data are presented in terms of adsorption, desorption. and structural properties, and their compatibility is discussed. Potassium forms (2 × 2) and $\text{(}\text{3}\text{×}\text{3}\text{)R30°}$ overlayers below and near monolayer coverage, and multilayer bonding and desorption is similar to that of bulk K. The initial sticking coefficients for CO adsorption on K predosed surfaces are correlated with the initial K structure, and s₀ and CO saturation coverages decrease with increasing K coverage. Two well-characterized mixed CO+K layers have been found which are correlated with predosed (2 × 2) K and $\text{(}\text{3}\text{×}\text{3}\text{)R30°}\text{K}$. They have CO to K ratios of 3:2 and 1:1, and lead to LEED patterns with (2 × 2) and (3 × 3) symmetry, respectively. The molecule is believed to be sp² rehybridized under the influence of coadsorbed K, leading to stronger CO-Ru and weaker C-O bonds as indicated by the TPD and HREELS results, and to stand upright in essentially twofold bridges.     

The influence of CO adsorption on the galvanomagnetic and magnetic properties of evaporated nickel films

The influence of CO adsorption on the ordinary Hall coefficient, R_HO, the extraordinary Hall coefficient, R_HE, the perpendicular magnetoresistivity ΔR_{mag O} and the saturation magnetization, B_S, of Ni films with thicknesses between 1 and 200 nm has been studies as a function of the CO coverage at 77 and 273 K. There is a maximum in ΔR_HE at a coverage of about half a monolayer. ΔR_HO, ΔΔR_{mag O} and ΔB_S exhibit an oscillating behaviour.     

Elucidation of surface structure and bonding by photoelectron spectroscopy?

Information obtained on the adsorption of small and medium-sized molecules (CO, O₂, CO₂, NO, C₂H₄, C₆H₆) at three metal surfaces (Mo, W, Ni) by X-ray photoelectron spectroscopy (XPS) and ultra-violet photoelectron spectroscopy (UPS) is discussed in an attempt to establish what has been achieved, and what might be achieved in the elucidation of adsorption bonding at metal surfaces. Some of the individual results have been published by the present author with co-workers, and by other authors, but some results represent new work. Emphasis is placed on the detection of different states of adsorption, and then on interpretations of structure and bonding. The latter is divided into two areas, empirical interpretation by analogy between different adsorption systems, and in more absolute terms by consideration of the differences in electronic energy levels between the absorbate molecule in its gaseous and adsorbed state as well as differences between the metal levels in the clean and surface bonded state. Note is made of the problems of suitable reference levels and the phenomena of relaxation energies. Mo and W are taken as representative examples of adsorption confined usually to the monolayer regime; Ni is taken as an example of the situation where further reaction may occur. Most of the work described refers to polycrystalline films since little work has yet been done by XPS on adsorption at single crystal surfaces. A short general review of the quantitative aspects of XPS and UPS for analysis is given.     

ESR and Chemical Bonding of Some Copper Complexes

ESR spectra of copper (II) was measured in 33 copper complexes which were synthesized in this laboratory and the bonding parameter α²of copper was calculated according to the method proposed by Kivelson. ⁽¹⁾ The results of these calculations are classified, together with the data quoted from the literature,^1-5into four groups according to the kinds of ligand atoms, i.e., α²is 0.72 to 0.87 for 0₄ - type complexes, 0.69 to 0.86 in N₂O₂, 0.74 to 0.82 in N₄, and 0.54 to 0.62 in S₄ and S₂₃N₂ type complexes, where 0, H and S refer the oxygen, nitrogen and sulfur atoms of ligands, respectively, that directly coordinate with copper.     

An XPS and UPS study of the interaction of oxygen with sodium-dosed Ag(110)

The adsorption of Na and the coadsorption of Na and O₂ on Ag(110) have been studied by XPS and UPS. Adsorption of Na results in a rapid decrease in the work function. Δφ reaching a limiting value of ?2.0 eV at θ_Na = 0.5 and thereafter remaining constant. In the coverage range 0 < θ_Na <1 adsorption of O₂ onto the Na dosed surface always results in an increase in the work function to an almost constant value of Δφ ~ ?1 eV. At the same time the XPS data show that the Na/O stoichiometry of the oxygen saturated surface remains essentially constant and independent of the initial Na dose. Calibration experiments using sodium formate as a standard compound indicate that this surface phase has the stoichiometry Na₂O. For θ_Na > 1 there is a sharp change in behaviour; the work function of the oxygen saturated surface begins to decrease rapidly, and eventually falls below the value for the Na covered surface itself at θ_Na ~ 1.5. The XP spectrum now shows the appearance of a new oxygen peak which increases in intensity as θ_Na increases beyond unity. The UP spectra indicate that the binding energy of the surface orbital derived from Na (3s) is increased by ~6.7 eV as compared with the free atom value, and the emission at ~3 eV below E_F, which is associated with surface oxygen is not greatly affected by the presence of Na. These results are discussed against the background of information already available from LEED, Auger, and thermal desorption studies, and we attempt to give a consistent interpretation of the properties of the system at coverages both below and above one monolayer.     

CO2 adsorption on Cr(1 1 0) and Cr2O3(0 0 0 1)/Cr(1 1 0)

We attempt to correlate qualitatively the surface structure with the chemical activity for a metal surface, Cr(1 1 0), and one of its surface oxides, Cr₂O₃(0 0 0 1)/Cr(1 1 0). The kinetics and dynamics of CO₂ adsorption have been studied by low energy electron diffraction (LEED), Aug er electron spectroscopy (AES), and thermal desorption spectroscopy (TDS), as well as adsorption probability measurements conducted for impact energies of E_i = 0.1-1.1 eV and adsorption temperatures of T_s = 92-135 K. The Cr(1 1 0) surface is characterized by a square shaped LEED pattern, contamination free Cr AES, and a single dominant TDS peak (binding energy E_d = 33.3 kJ/mol, first order pre-exponential 1 × 10¹³ s⁻¹). The oxide exhibits a hexagonal shaped LEED pattern, Cr AES with an additional O-line, and two TDS peaks (E_d = 39.5 and 30.5 kJ/mol). The initial adsorption probability, S₀, is independent of T_s for both systems and decreases exponentially from 0.69 to 0.22 for Cr(1 1 0) with increasing E_i, with S₀ smaller by ∼0.15 for the surface oxide. The coverage dependence of the adsorption probability, S(Θ), at low E_i is approx. independent of coverage (Kisliuk-shape) and increases initially at large E_i with coverage (adsorbate-assisted adsorption). CO₂ physisorbs on both systems and the adsorption is non-activated and precursor mediated. Monte Carlo simulations (MCS) have been used to parameterize the beam scattering data. The coverage dependence of E_d has been obtained by means of a Redhead analysis of the TDS curves.     

Coordination of acetonitrile (CH3CN) to platinum (111): Evidence for an η2(C,N) species

Acetonitrile (CH₃CN) coordination to a Pt(111) surface has been studied with electron energy loss vibrational spectroscopy (EELS), XPS, thermal desorption and work function measurements. We compare data for the surface states with known acetonitrile coordination complexes. For CH₃CN adsorbed on Pt(111) at 100 K, the molecule is rehybridized and adsorbs with the CN bond parallel or slightly inclined to the surface plane in an η²(C, N) configuration. The ν(CN) frequency is 1615 cm^?1 and the C ls and N ls binding energies are 284.6 eV and 397.2 eV respectively. By contrast, weakly adsorbed multilayer acetonitrile exhibits a ν(CN) vibrational frequency of 2270 cm^?1, and C ls and N ls binding energies of 286.9 eV and 400.1 eV respectively. Both the EELS and XPS results are consistent with rehybridization of the CN triple bond to a double bond with both C and N atoms of the CN group attached to the surface. In addition to this majority η²(C, N) monolayer state, evidence is found for a second, more strongly bound minority molecular state in thermal desorption spectra. As a result of the low coverage of this state, EELS was unable to spectroscopically identify it and we tentatively assign it as an η⁴(C, N) species associated with accidental step sites. By contrast to the surface complexes, almost all of the known platinum-nitrile coordination complexes are end-bonded via the N lone-pair orbital. Several cases of side-on bonding are known, however, and we compare the results with the known complex Fe₃(η²-NCCH₃)(CO)₉. The difference in the coordinative properties of a Pt(111) surface versus a single Pt atom must be due to the increased ability of multi-atom arrays to back-donate electrons into the π¹ system of acetonitrile. Previously published EELS and XPS results for monolayer acetonitrile on Ni(111) and polycrystalline films are almost identical to the present results on Pt(111). We believe that the monolayer of $\text{CH}{}_3\text{CN}\text{Ni}\text{(111)}$ is also an η²(C, N) species, not an end-bonded species previously proposed by Friend, Muetterties and Gland.     

The interaction of dimethylsulfoxide with a gold surface

The interaction of dimethylsulfoxide (DMSO) with a Au(100) surface was studied by means of TDS, XPS and ΔΦ measurements. At monolayer coverages, DMSO desorbs from two states situated at the relatively high temperatures of 240 and 275 K. The adsorbed molecule, however, shows no chemical shifts in its core levels. This is rationalized by a bidentate bonding of DMSO to the surface through the electron lone-pairs on the O and S atoms. The adsorption geometry agrees also with the behavior of the work function (ΔΦ_DMSO = − 770 meV).     

Molecular and atomic adsorption states of oxygen on Cu(111) at 100–300 K

Adsorption states of oxygen on Cu(111) at 100–300 K were investigated by means of HREELS. Two molecular species were characterized by different OO stretching frequencies (v(OO)) at 610 cm⁻¹ and 820–870 cm⁻¹, which are assigned to the peroxo-like species (O²⁻₂) adsorbed in a bridged form and the one in a bidentate form bound on an atop site, respectively. The bridged peroxo species is preferred at the low coverage and the atop peroxo species becomes dominant at the higher coverage. In addition to the peaks due to the molecular oxygen, a peak assigned to v(CuO) of atomic oxygen was observed at 370 cm⁻¹ at the high coverage. The frequency of this mode was higher than the frequency reported for Cu(111) exposed to oxygen above 300 K, indicating that the adsorption state of atomic oxygen formed at 100 K is different from that above 300 K. The v(OO) modes became faint after annealing to 170 K because of O₂ dissociation. The v(CuO) mode of the atomic oxygen formed at 100 K remained up to 230 K and disappeared after annealing to 300 K. No desorption of O₂ was detected on annealing to 300 K. It was also found that vibrational spectra for adsorbed NH₃ are influenced by the adsorption states of atomic oxygen on Cu(111).     

Electronic and bonding properties of mono-ruthenium-substituted Keggin-type polyoxometalates: a theoretical study of [{PW11O39}RuII/III(L)] n − (L = dimethyl sulfoxide (DMSO), water,pyridine, and ammonia) and [{GeW11O39}RuII(DMSO)3(H2O)]6−

The electronic structure and bonding feature of a series of mono-ruthenium-substituted Keggin-type polyoxometalates (POMs) have been investigated by using density functional theory (DFT) calculation, natural bond orbital (NBO) analysis and energy-decomposition analysis (EDA). A comparison of the electronic properties of two known dimethyl sulfoxide (DMSO)-supported mono-ruthenium-substituted Keggin-type POMs shows that both complexes have the analogous frontier-molecular orbital feature. One of them possesses a relatively small HOMO–LUMO gap because of the high HOMO energy level. This difference comes from a high composition of POM ligand with antibonding feature in HOMO. In addition, three typical Keggin-type POM complexes [{PW₁₁O₃₉}Ru^II/III(L)]^n? (L = H₂O, C₅H₅N, NH₃) have also been explored according to our computational studies. The NBO analysis shows that the Ru^II/III–L bond comes from donor–acceptor interactions between the end ligand and the ruthenium (II/III) centre. The EDA shows that the POM complex [{PW₁₁O₃₉}Ru^II(C₅H₅N)]^5? has much stronger Ru^II–L bond than ammonia-supported Keggin-type POM [{PW₁₁O₃₉}Ru^II(NH₃)]^5?. And the enhancement of the Ru^II–L bonding interaction in [{PW₁₁O₃₉}Ru^II(C₅H₅N)]^5? is mainly due to the large orbital interaction energy ΔE_orb. The ammonia-supported Keggin-type POM [{PW₁₁O₃₉}Ru^II(NH₃)]^5? and the aqua-ruthenium derivative [{PW₁₁O₃₉}Ru^II(H₂O)]^5? have an analogous magnitude of the total bond energy. This result supports a non-aqueous environment for synthesis of an ammonia-supported Keggin-type POM [{PW₁₁O₃₉}Ru^II(NH₃)]^5?.     

The submillimeter wave spectrum of 32S16O2, 32S16O2(ν2), and 34S16O2

Extensive new measurements in the region 400–1000 GHz have been made on ³²S¹⁶O₂, ³²S¹⁶O₂(ν₂), and ³⁴S¹⁶O₂. These measurements represent almost a threefold extension in the frequency region for which high-resolution microwave data are available. These data have been combined with the previously available microwave data for this analysis. The results, when extrapolated into the far infrared, compare favorably with recent results obtained from high-resolution FIR spectroscopy.     

Interpretation of kinetics of iron surface oxidation involving the real structure of single crystal samples

The kinetics of oxidation of iron surface has been studied by AES method. The effects of oxygen diffusion into the lattice defects have been considered in the discussion of the mechanism of the oxygen adsorption. The real sticking coefficient has been determined as a function of oxygen coverage (S=1?θ in the range of 0<θ<0.9). The oxidation of iron surface occurs in two steps. At the first step the dissociative oxygen adsorption occurs for the coverage 0<θ _O<1 and the rate of the oxygen molecule adsorption is limiting. At the second step, in the range of oxygen coverage 1<θ _O<2, the reconstruction of the iron surface occurs with the formation of free adsorption sites. At this step the sticking coefficient of oxygen is almost constant (S≈0.1).     

Intensity of the atomic oxygen lines at 8446 and 7771 A in an Ar-O2 d.c. glow discharge

An equation for the intensity ofO(3³P?3³S) at 8446 A and ofO(3⁵P?3⁵S) at 7771 A has been derived as a function of electron-, Ar- and O₂-densities assuming applicability of the excitation processes proposed by Bennett et al. and by Tunitskii and Cherkasov. The electron temperature has been assumed to be constant. The results are compared with experimental data obtained in the d.c. glow discharge of Ar-O₂ mixtures.     

Photocorrosion of cadmium sulfide: Analysis by photoelectron spectroscopy

Photocorrosion of cadmium sulfide electrodes in aqueous electrolytes leads to sulfate formation in the presence and to sulfur formation in the absence of oxygen. All three sulfur species involved (S²⁻, S⁰ and SO²⁻₄) can be detected on CdS electrodes after treatment in photoelectrochemical cells using AES or XPS. Both, the S2p/3p XPS and the S Auger peaks are broadened on photoelectrochemical oxidized CdS due to deposition of elemental sulfur. The XPS binding energy of the S electrons is shifted by about 1 eV per sulfur oxidation step from around 161.5 eV for S²⁻ to around 163.5 eV for S⁰ and around 168 eV for SO²⁻₄. The results obtained by photoelectron spectroscopy of electrodes transferred from the electrolyte directly into the UHV system without any cleaning and special precautions are in excellent agreement with the predictions based on photoelectrochemical experiments. For example, it could be proved by XPS that sulfur was transformed into sulfate in a reductive oxidation step in the presence of oxygen, leading to the CdS surface being cleaned of S⁰.     

Site-specific interaction of H2O with ZnO single-crystal surfaces studied by thermal desorption and UV photoelectron spectroscopy

The adsorption and condensation of H₂O(D₂O) on ZnO(101&#x0304;0), (0001)Zn and (0001&#x0304;)O surfaces was investigated by means of thermal desorption (TDS) and UV photoelectron spectroscopy (UPS). The clean ZnO single-crystal surfaces were prepared by Ar-ion sputtering and annealing and characterised by Auger electron spectroscopy, LEED, UPS and work-function measurements. On all three surfaces six different adsorption states were found. In the monolayer regime there is a stronger bonding to Zn sites (desorption temperature 340 K) than to O sites (190 K), The bonding to the Zn sites seems to be accompanied by some clustering. Before the chemisorption layer is completed a first ice state is found whose desorption temperature shifts from 162 to 168 K with increasing exposures. At higher exposures the multilayer ice state is found at 152 K. On the (0001&#x0304;)O face defect-induced features were identified. The water lone-pair orbital 1b₁, whose energy falls between the O p and the Zn 3d emission of the substrate and which is known to show bonding shifts, was analysed using angle-resolved UPS. In the monolayer, the main chemisorption states are found at E_B^V(1b₁) = ?9.6 eV for the (0001)Zn face and at ? 10.6 eV for the (0001&#x0304;)O face and are compared with the multilayer ice emission at 1&#x0304;1.1 eV. The difference in binding energies shows the same trend as the TDS data. For the (101&#x0304;0) face the 1b₁ emission is very broad, indicating some overlap between different states.     

Adsorption dynamics of CO2 on Cu(1 1 0): A molecular beam study

Molecular beam scattering measurements have been conducted to examine the adsorption dynamics of CO₂ on Cu(1 1 0). The initial adsorption probability, S₀, decreases exponentially from 0.43 ± 0.03 to a value close to the detection limit (∼0.03) within the impact energy range of E_i = (0.12-1.30) eV. S₀ is independent of the adsorption temperature, T_s, and the impact angle, α_i, i.e., the adsorption is non-activated and total energy scaling is obeyed. The coverage, Θ, dependent adsorption probability, S(Θ), agrees with precursor-assisted adsorption dynamics (Kisliuk type) above T_s ∼ 91 K. However, below that temperature adsorbate-assisted adsorption (S increases with Θ) has been observed. That effect is most distinct at large E_i and low T_s. The S(Θ) data have been modeled by Monte Carlo simulations. No indications of CO₂ dissociation were obtained from Auger Electron Spectroscopy or the molecular beam scattering data.