Adsorption of CO on clean and oxygen covered Ni(111) surfaces

Adsorption of CO on Ni(111) surfaces was studied by means of LEED, UPS and thermal desorption spectroscopy. On an initially clean surface adsorbed CO forms a √3 × $\text{√3}\text{R30°}$ structure at θ = 0.33 whose unit cell is continuously compressed with increasing coverage leading to a c4 × 2-structure at θ = 0.5. Beyond this coverage a more weakly bound phase characterized by a $\text{√7}\text{2}$ × $\text{√7}\text{2R19°}$ LEED pattern is formed which is interpreted with a hexagonal close-packed arrangement (θ = 0.57) where all CO molecules are either in “bridge” or in single-site positions with a mutual distance of 3.3 Å. If CO is adsorbed on a surface precovered by oxygen (exhibiting an O 2 × 2 structure) a partially disordered coadsorbate 2 × 2 structure with θ_o = θ_co = 0.25 is formed where the CO adsorption energy is lowered by about 4 kcal/mole due to repulsive interactions. In this case the photoemission spectrum exhibits not a simple superposition of the features arising from the single-component adsorbates (i.e. maxima at 5.5 eV below the Fermi level with O_ad, and at 7.8 (5σ + 1π) and 10.6 eV (4σ) with CO_ad, respectively), but the peak derived from the CO 4σ level is shifted by about 0.3 eV towards higher ionization energies.     

The He(I) photoelectron spectroscopy of heavy group IV—VI diatomics

The He(I) photoelectron spectra of the Group IV—VI diatomics GeO, GeS, GeSe, GeTe, SnS, SnSe, and SnTe are presented. The outermost valence structure of these molecules is similar to that observed in the lighter series CO, CS, etc. of this valence isoelectronic group; in each case a relatively sharp peak is assigned to ionization from the nominally non-bonding 3σ orbital and a broader band to ionization from the bonding 1π orbital. At higher binding energies the spectra exhibit several peaks where only a single peak is expected, from the (2σ)^?1 hole state. This structure is assigned to correlation peaks resulting from configuration interaction among hole states of ²Σ⁺ (Ω = $\text{1}\text{2}$) symmetry. Semi-empirical CNDO—MO calculations have been performed for these molecules, and the results are used to interpret the observed trends. In addition, a simple molecular orbital model is employed to estimate the importance of spin—orbit coupling in the valence electronic structure of the heavy IV—VI ions.     

Comments on “the chemisorption and decomposition of no on the (110) surface of iridium” by D.E. Ibbotson,T.S. Wittrig and W.H. Weinberg

In a recent paper by Ibbotson et al. [Surface Sci. 110 (1981) 294] the chemisorption of NO on Ir(110) was studied with Hel UV photoelectron spectroscopy, amongst other techniques. For molecular adsorption, the levels observed at 13.5, 10.4 and 8.5 eV below the Fermi level were associated with the 4σ, 5σ and 1π orbitais of NO, respectively. It is proposed that such a specific assignment is not possible, rather that the observed levels are due to photoemission from (5$\text{}\text{?}$gs + 1g?p). Some other errors in the literature regarding the assignment problem are also discussed.     

Molecular cluster calculations for the interpretation of CO chemisorption on a Ni(100) surface

Self-consistent Hartree-Fock-Slater molecular cluster calculations for the chemisorption of carbon monoxide on a Ni(100) surface are presented. In earlier calculations of this type the CO molecule has been assumed to be chemisorbed in a hollow position of C_4v symmetry. A recent EELS experiment shows however that in the most stable configuration CO is linearly bonded to the Ni atoms, i.e. a top position of the CO-molecule. This experiment indicates also that there exists an additional bridge bonding of the CO molecule to the two nearest neighbour Ni atoms. The variation of the energy levels, binding energies and charge distribution with the height of the CO molecule above the nickel surface is calculated for the top position using the NiCO and Ni₅CO clusters and for the bridge bonding configuration using the Ni₂CO cluster. The CO 1π level is found to be split by about 0.8 eV in bridge bonding geometry. For both hollow and top positions the 1π and 5σ levels are separated by about 0.5 eV. The energy separation to the 4σ level is about 3 eV, which is in good agreement with experimental data. Theoretical ionization energies relative to the Fermi energy for top position geometry at a bond distance of 3.5 au between the carbon atom and nickel surface were found to be 25.7, 11.7, 8.7 and 8.2 eV for the 3σ, 4σ, 5σ and 1π levels which should be compared with the experimental data of 29.0, 10.8, 8.4 and 7.8 eV, respectively. The corresponding ionization energies for a bond angle of 99° in bridge bonding were 23.7, 12.1, 7.3, 7.0 and 7.9 eV. The two last values represent the 1π level which is split into two levels in this geometry. The variation of the C-O stretch vibrational frequencies with the height of the CO molecule above the surface for the top-position geometry is estimated from the 5σ and 2π gross orbital populations and from the CO σ and π overlap populations.     

The interaction of oxygen with gadolinium: UPS and XPS studies

The interaction of oxygen with evaporated Gd films at 300 K has been studied for the first time using AlK α XPS and Hel and Hell UPS. The characteristic changes in the Gd(6s5d) and O(2p) valence bands, Gd(4f), Gd(5p) and Gd(4d) core levels, and O(2s) and O(1s) core levels were studied. Evidence is presented for the initial formation of an intermediate oxidation state at low exposure (characterized by a new Gd valence band with a maximum in the DOS at ～ 2.5 ev below E_F and an ～ 0.6 eV shift in Gd(4f)) prior to formation of Gd₂O₃ where the Gd(6s5d) valence band disappears completely, as expected for Gd³⁺. In the higher exposure range there is little further increase in the oxide thickness, which is estimated as $\text{? 20}\text{A}\text{?}$, but there is a slow replacement of O by OH, as characterized by a second O(1s) feature at 532.3 eV and OH 1π and 3σ orbitals in UPS at ～ 6.7 and 11.5 eV. The interpretations are supported by parallel studies on bulk Gd₂O₃ and by Ar⁺ sputtering experiments. Comparisons are made to other rare earth oxidation studies.     

Deposition of nickel from Ni(CO)4 on palladium and iron surfaces studied by X-ray photoelectron spectroscopy

The interaction of nickel carbonyl, Ni(CO)₄, with evaporated palladium and iron surfaces has been studied at 90 and 290 K by X-ray photoelectron spectroscopy. The carbonyl is weakly adsorbed in molecular form at 90 K on the metals giving a $\text{Ni 2p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ peak at 854.6 eV, a C 1s at 287.2 eV and an O 1s at 533.8 eV. Some fraction of the carbonyl decomposes even at 90 K on iron to give deposited nickel atoms. In the interaction with palladium at 290 K, deposited nickel atoms $\text{(Ni 2p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{= 852.9 eV)}$ and chemisorbed CO are observed. A satellite feature of the $\text{Ni 2p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ peak varies depending on the quantity of the deposited nickel atoms; the main peak-satellite separation increases with increase in the quantity. The same variation is observed for evaporated nickel-palladium alloys. This can be ascribed to the difference in the electronic states of the nickel atoms. The difference is reflected in the reactivity of the atoms with O₂. With iron the deposited nickel atoms show an increase in binding energy of 0.4 eV in the $\text{Ni 2p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ Peak and no satellite when the number of nickel atoms is small. The oxidation of the surface is also studied.     

Photoelectron and electron impact spectrum of HCN

The electronic structures of HCN and DCN have been determined by examining high resolution He(I) photelectron spectra of HCN and DCN, He(II) photoelectron spectrum of HCN, and the electron impact energy loss spectra of HCN and DCN. The present investigation supports an earlier assignment of the orbital sequence in HCN. New vibrational data are presented and the Rydberg series and valence transitions are reinvestigated. The adiabatic ionization energies for the 1π and 5σ orbitals in HCN are found to be 13.607 ± 0.002 eV and 14.011 ± 0.003 eV respectively.As mentioned above the investigation of the Rydberg series indicated that the first IP at 13.607 eV is the 1π ionization and the second IP at 14.011 eV is the 5σ ionization. A comparison of the experimental and theoretical intensity ratio between the two first PES progressions also supports this assignment. It is further supported by the fact that in the second IP the ν₃ vibration frequency is not changed as much as it is in the first IP, which is in agreement with the PES of N₂ and CO. The analysis of the bending vibrations also supports this ordering of the orbitals.The same orbital assignment has recently been proposed by Frost et al.⁵, using a comparison with the HCP photoelectron spectrum. The present paper supports their assignment of orbitals and (00⁰0)-(00⁰0) transitions. There are, however, some disagreements concerning the vibrational analysis. This is probably due to the fact that the HCN spectrum of Frost et al.⁵ revealed less structure than ours. As indicated by Figure 5 there is possibly still more structure to be revealed.     

Delayed onset of 4d photoemission relative to the giant 4d photoabsorption of La

For the giant 4d photoabsorption of La, both the total photoabsorption spectrum and the N_4.5-derived Auger emission intensity spectrum increase significantly above hν ? 112 eV, with spectral peaks at hν = 118 and 119 eV, respectively. However, the predominant 4d photoemission partial cross section shows a delayed onset of ～ 4 eV, with a peak at hν = 121 eV, while the 5s, 5p, and 5d partial cross sections all show a strong resonant enhancement at lower energies, with spectral peaks at hν = 116.6 eV. These results are compared with a recent many-body calculation for Ce. The photon energy dependence of the La 4d_{$\text{5}\text{2}$}/4d_{$\text{3}\text{2}$} photo-emission branching ratio is consistent with a “final-state model.”     

Photoemission of Xe and Kr adsorbed on the W(110) plane

The UPS and XPS spectra of Xe adsorbed on clean, O, CO, and Xe covered W(110) surfaces and the UPS spectrum for Kr on clean and O covered W(110) surfaces have been investigated. On clean W, Xe and Kr show a splitting of the $\text{5p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ and $\text{4p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ hole states respectively. For Xe the coverage dependence of this splitting was investigated in detail; neither the positions nor the intensity ratio of the substates are coverage dependent for θ ? 0.04, suggesting that splitting is due to differences in the image interaction of the $\text{m}{}_{\mathrm{j}}\text{= ±}\text{3}\text{2}$ and $\text{m}{}_{\mathrm{j}}\text{= ±}\text{1}\text{2}$ components. For Xe equal shifts, relative to vacuum, of ~1.0 eV were observed for 5p, 4d, and 3d levels, suggesting that initial state effects are small. Image interaction for Xe and Kr on clean W could best be fitted by assuming an increase, rather than a decrease in the effective hole-image separation from the nominal value, suggesting that the image plane is moved back into the metal by a screening length. For Xe adsorbed on $\text{Xe}\text{W}$(110), or on virgin-$\text{CO}\text{W}\text{(110)}$ polarization of the intermediate layers was found to contribute significantly to relaxation. Coadsorbed oxygen broadened Xe 5p and Kr 4p peaks. There was an almost linear relation between O 2p UPS intensity at the energies of the various peaks and the amounts of broadening, suggesting that the latter results from resonance neutralization by electrons from the O 2p states.     

Photoemission of adsorbed CO and H2O on Pt: Valence band studies

In this paper, using monochromatic He and Ne discharge lines, we report the ultraviolet photoemission results for CO and H₂O adsorbed on a Pt crystal. For chemisorbed CO, we use the energy dependence of the photoionization cross section to deduce that the 5σ?1π splitting is approximately 1 eV and that the 5σ is located at about ?8.1 eV while the 1π is at ?9.1 eV. The distribution of metal electrons changes in two ways upon CO chemisorption: a d character peak is found at ?4 to ?5 eV and emission at E_f is strongly depleted. For the weakly adsorbed water molecule, we find preferential attenuation of Pt states near E_f that has heretofore been observed for strongly chemisorbed systems.     

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.     

A study of the (00) LEED beam intensity at normal incidence from CdS(0001), Cu(001), Cu(111), and Ni(111)

A Faraday cage apparatus is used for the measurement of the (00) LEED beam intensity, I₍₀₀₎, and the total secondary emission coefficient, δ(E_k), for angles of incidence from 0° ± 2° to 8° ± 2°, with an energy resolution of ± 0.037 of the incident beam energy, in the energy range 1 to 200 eV. The data are normalized and expressed as a fraction of the incident beam intensity. The basic principle of operation is the separation of the incident and specularly diffracted beams in a uniform magnetic field. Monolayer, or in-plane, resonances associated with the emergence of nonspecular beams, as well as beam threshold minima, are observed in I₍₀₀₎ at normal incidence from clean CdS(0001), Cu(111), and Ni(111). Some major differences are observed in the I₍₀₀₎ profiles for the clean (111) surfaces of nickel and copper. All secondary Bragg peaks, except the 2$\text{2}\text{3}$ order, have greater intensities for Ni(111) in the energy range 50–150 eV, thus indicating that the atomic scattering cross-section for electrons in this energy range is larger for nickel than for copper. For the (111) surface of nickel, the (11) resonance is missing, but the (10) resonance and all $\text{1}\text{3}$ order secondary Bragg peaks between the second and fifth orders are observed. For Cu(111) both the (10) and (11) resonances are observed, but the $\text{1}\text{3}$, $\text{2}\text{3}$, 1$\text{2}\text{3}$, and 3$\text{1}\text{3}$ order secondary Bragg peaks are missing in this energy range. These data indicate that multiple scattering with evanescent intermediate waves, or “shadowing”, is predominate on the (111) surfaces on nickel and copper for energies above 30 eV, and that below 30 eV multiple scattering with propagating intermediate waves is predominate on Cu(111). Correlation of the (00) beam intensity profiles from clean Ni(111) at 0°, 2°, and 6° with the intensity profiles of the (10). (1&#x0304;0), and (11) non-specular beams is nearly one-to-one from 30 eV to 100 eV, thus supporting the dynamical theories of LEED in which peaks in the (00) beam are expected to occur at nearly the same energies as peaks in the non-specular beams.     

Kerr-effect and dielectric tensor elements of magnetite (Fe3O4) between 0.5 and 4.3 eV

The complex polar Kerr effect (rotation and ellipticity) of magnetite single crystals has been measured at room temperature between 0.5 and 4.3 eV. From the magneto-optical data and the optical constants, the off-diagonal elements (?_xy) of the dielectric tensor has been derived. Three well separated magneto-optical transitions have been indentified. At about 0.75 eV one strong magneto-optical structure with a diamagnetic line shape is assigned to a $\text{3d}{}^6\text{→3d}{}^5\text{(}{}^6\text{A}{}_{\mathrm{1g}}\text{) 4s}$ transition from Fe²⁺ in octahedral sites. Two other structures with paramagnetic line shapes near 1.85 and 2.90 eV are assigned to the orbital promotion processes $\text{3d}{}^6\text{(Fe}{}^{\mathrm{2+}}{}_{\mathrm{oct}}\text{)→3d}{}^5\text{(}{}^4\text{T}{}_{\mathrm{1g}}\text{) 4s}$ and $\text{3d}{}^5\text{(Fe}{}^{\mathrm{3+}}{}_{\mathrm{tet}}\text{)→3d}{}^4\text{(}{}^5\text{T}{}_2\text{) 4s}$, respectively, which take into account Fe 3d^n?1 final state effects.     

Dielectric constants of adsorbed CO on Cu and Ag

Adsorption of CO on evaporated Ag and Cu films was studied by ellipsometry and resistivity measurements. Changes in ellipsometric angles δΔ and δψ due to adsorption of CO were analyzed by an improved linear approximation of the stratified layer model of adsorption. Adsorption of CO on Cu induced a 23% increase in the relative resistivity change (δR/R) which was proportional to δψ, while adsorption of CO on Ag induced a 1% increase without the proportionality. The dielectric constant of CO adsorbed on Ag is $\text{?}{}_1\text{= 2.2?0.7i}$ at λ = 1152 nm in comparison to ?₁ = 2.1 for gas phase CO; that of CO on Cu is $\text{?}{}_1\text{= ?4.8 ? 8.5i}$, which is consistent with the prediction by the Bennett and Penn theory. The large difference in $\text{}\text{?}$ge₁, of adsorbed CO on Ag and Cu is understood in terms of the energy level of the 2 π molecular orbital of adsorbed CO relative to the Fermi level. A possibility of adlayer plasmon excitation is discussed.     

Valence shell momentum distributions,binding energies,and calculated wavefunction evaluation for H2S by binary (e,2e) spectroscopy

We report preliminary results on the binding energy spectrum and molecular orbital momentum distributions of H₂S as measured by binary (e,2e) spectroscopy at 400 eV. Extensive final ion state structure associated with ionization from the inner valence molecular orbital of H₂S is observed. Three momentum distribution calculations for H₂S using basis sets of varying complexity show a better fit than in H₂O (J. Electron Spectrosc. $\text{11}$ (1977) 205) for a given quality of basis set.     

A density functional theory study on the adsorption of CO and O2 on Cu-terminated Cu2O （111） surface

The adsorptions of CO and 02 molecules individually on the stoichiometric Cu-terminatcd Cu20 （111） surface are investigated by first-principles calculations on the basis of the density functional theory. The calculated results indicate that the CO molecule preferably coordinates to the Cu2 site through its C atom with an adsorption energy of-1.69 eV, whereas the 02 molecule is most stably adsorbed in a tilt type with one O atom coordinating to the Cu2 site and the other O atom coordinating to the Cul site, and has an adsorption energy of -1.97 eV. From the analysis of density of states, it is observed that Cu 3d transfers electrons to 2π orbital of the CO molecule and the highest occupied 5σ orbital of the CO molecule transfers electrons to the substrate. The sharp band of Cu 4s is delocalized when compared to that before the CO molecule adsorption, and overlaps substantially with bands of the adsorbed CO molecule. There is a broadening of the 2π orbital of the 02 molecule because of its overlapping with the Cu 3d orbital, indicating that strong 3d-2π interactions are involved in the chemisorption of the 02 molecule on the surface.     

Low energy electron diffraction and electron spectroscopy studies of the clean (110) and (100) titanium dioxide (rutile) crystal surfaces

Low-energy electron diffraction (LEED), Auger electron spectroscopy (AES), electron energy loss (ELS) and ultraviolet photoemission spectroscopies (UPS) were used to study the structures, compositions and electron state distributions of clean single crystal faces of titanium dioxide (rutile). LEED showed that both the (110) and (100) surfaces are stable, the latter giving rise to three distinct surface structures, viz. (1 × 3), (1 × 5) and (1 × 7) that were obtained by annealing an argon ion-bombarded (100) surface at ~600,800 and 1200° C respectively. AES showed the decrease of the $\text{O(510 eV)}\text{Ti(380 eV)}$ peak ratio from ~1.7 to ~1.3 in going from the (1 × 3) to the (1 × 7) surface structure. Electron energy loss spectra obtained from the (110) and (100)?(1 × 3) surfaces are similar, with surface-sensitive transitions at 8.2, 5.2 and 2.4 eV. The energy loss spectrum from an argon or oxygen ion bombarded surface is dominated by the transition at 1.6 eV. UPS indicated that the initial state for this ELS transition is peaked at ?0.6 eV (referred to the Fermi level E_F in the photoemission spectrum, and that the 2.4 eV surface-sensitive ELS transition probably arises from the band of occupied states between the bulk valence band maximum to the Fermi level. High energy electron beams (1.6 keV 20 μA) used in AES were found to disorder clean and initially well-ordered TiO₂ surfaces. Argon ion bombardment of clean ordered TiO₂ (110) and (100)?(1 × 3) surfaces caused the work function and surface band bending to decrease by almost 1 eV and such decrease is explained as due to the loss of oxygen from the surface.     

Coverage and adsorption-site dependence of core-level binding energies for tin and lead on Al(111) and Ni(111)

Thin layers (0.2–10 monolayers) of Pb and Sn were prepared on Al(111) and Ni(111) surfaces and characterized by means of LEED, AES, UPS and work-function measurements. The binding energy of the shallow Sn 4d and Pb 5d core-levels was investigated with respect to coverage and adsorption-site-dependent changes. On Al(111) the Sn and Pb monolayers exhibit ordered, two-domain, aligned but not in registry structures. For these layers core-level binding energies were found identical to those of the bulk metals. On Ni(111), Pb gives rise to a 3 × 3 structure, followed then by a 4 × 4 structure at higher coverages. The Pb 5d core-level binding energies shift continuously to higher values. A final shift of 0.42 eV is reached after about 2 monolayers. Sn on Ni(111) exhibits two welll separated peaks lying at 23.70 and 23.97 eV for the $\text{4d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$ line. These two lines can be correlated with two different adsorption sites which have to be assumed for the $\text{(}\text{3}\text{×}\text{3}\text{)R30°}$ and the (2 × 2) structure found at different coverages. The binding energy shifts are discussed in a model based on a Born-Haber cycle.     

On the interaction of cesium with cleaved GaAs(110) and Ge(111) surfaces: Work function measurements and adsorption site model

The work function of UHV cleaved p-Ge(111) and n-GaAs(110) surfaces has been measured in dependence of the Cs coverage. At very low coverages θ < 0.001 the decrease of the contact potential difference is extremely steep. For GaAs the initial slope of the CPD versus coverage curve amounts to ?740 eV for Ge to ?130 eV per monolayer. Up to the saturation coverage the curves exhibit straight line segments with breaks at distinct coverages. Breaks are found for GaAs at approximately $\text{1}\text{12}$, $\text{1}\text{6}$, and $\text{1}\text{3}$ of a monolayer, for Ge at about $\text{1}\text{12}$, $\text{1}\text{4}$, $\text{1}\text{2}$, and $\text{3}\text{4}$. A new model is developed to explain this behaviour. It is based on the assumption of specific adsorption sites for the Cs atoms at the surfaces. With this model the experimental results, including the breaks, may be described in the whole coverage range from θ = 0.03 up to the saturation. Furthermore the dipole moments derived from the straight line segments are in excellent agreement with those values calculated for different surface molecules between the adsorbed cesium and substrate atoms at the specific adsorption sites.