A model of ethylene and acetylene adsorption on the (111) surfaces of platinum and nickel

Despite the application of a variety of surface sensitive techniques to the adsorption of simple hydrocarbons on well characterized metallic surfaces, no consistent picture has appeared. We review briefly the published spectroscopic results of ultraviolet photoelectron spectroscopy (UPS) and electron energy loss spectroscopy (EELS) which probe, respectively, the electronic and vibrational structure of the surface-molecular complex, and we consider appropriate free molecular analogues, not only in their ground state but also in their first excited states. A simplified approach to determine the chemisorption geometry from UPS level shifts and EELS is presented. The technique allows an isolation of distortion induced shifts from the total relaxation shift, and we find that the true relaxation shift is rather constant, approximately 2.1 eV for the cases considered. These shifts can then be used to estimate the distance of the molecule to the surface. We concentrate primarily on four systems, C₂H₂ and C₂H₄ on Ni(111) and Pt(111), adsorbed at low temperature (below the onset of dissociation). Depending on the metal, the hydrocarbon can adsorb in a di-σ arrangement or with a distortion resembling the lowest energy configuration of the first excited state of the free molecule. We also consider briefly C₂H₄ on Ag and Cu in which no distortion occurs. The distortions that resemble the first excited states might occur as a consequence of donation of bonding (backbonding) electrons from (to) the normally filled π (empty π¹) to (from) the empty (filled) d-band states of the metal. The net effect on the hydrocarbon to partially empty the π level and fill the π¹ level, is analogous to a low excitation of the free molecule, π → π¹. For C₂H₄ (planar in the ground state), the lowest excitation is the triplet T-state (3–4 eV) of minimal energy for a 90° twisted configuration with a lengthened C-C bond. Acetylene is a linear molecule in the ground state, but cis- or trans-bent for the triplet excitations, ~a (5.2 eV) or ~b (6.0 eV), respectively. Chemisorbed geometries derived from these configurations seem possible for C₂H₄ on Ni(111) and C₂H₂ on Pt(111), while interchanging the adsorbates and substrates gives di-σ bonding, (sp³ hybridization), as proposed previously in the literature. For C₂H₄ on Ni(111), two of the hydrogens are twisted into the surface which leads to a softening of the CH vibrational frequency. For the four systems considered, the data are consistent with the C-C bond essentially parallel to the surface, but tilted orientations are not ruled out. While the models are clearly oversimplified, they suggest an interesting point of departure for likely chemisorption geometries. Also, some intriguing correspondences to the (presumed) location of the normally empty π¹ level and the d-band are noted.     

Structure and electronic factors in benzene coordination to Cr(CO)3 and to cluster models of Ni,Pt, and Ag (111) surfaces

Bonding of benzene to a chromium tricarbonyl fragment and to cluster models of silver, nickel, and platinum (111) surfaces is found by means of molecular orbital calculations to be dominated by a benzene donation bond involving its π (e_1g) orbitals and metal d orbitals. Three-fold hollow sites on the clusters are calculated to be most stable for benzene coordination, a conclusion reached in a number of experimental studies of benzene on metal surfaces. On the Ag, Ni, and pt clusters, the benzene CH bonds are found to bend away from the surface by ?2°, 8° and 19°, respectively, a result of carbon atom hybridization to maximize overlap with metal orbitals. For benzene chromium tricarbonyl, the CH bonds are calculated to bend 3° toward the metal, compared to a 1.7° bend reported in a diffraction study. The direction and magnitude of the CH bending are shown to depend on the metal d orbital occupancy (an electronic factor) and the proximity of metal atoms in the adsorption site (a structure factor). Small Kekulé distortions are calculated for the chromium complex and for the C_3v sites on Pt(111). Finally, recent experimental studies showing a decrease in benzene adsorption energy when potassium is coadsorbed on Pt(111) may be understood to result from decreased π donation which accompanies the shift up of the metal d band with cathodic charging.     

Benzene adsorption on nickel (100) and (111) faces studied by leed and high resolution electron energy loss spectroscopy

Studies of benzene (C₆H₆ and C₆D₆) adsorption have been performed by high resolution electron energy loss spectroscopy (HRELS) and LEED experiments on nickel (100) and (111) single crystal faces at room temperature. Chemisorption induces ordered structures, c(4 × 4) on Ni(100) and (2√3 × 2√3)R30° on Ni(111), and typical energy loss spectra with 4 loss peaks accurately identified with the strongest infrared vibration bands of the gazeous molecules. Benzene chemisorption preserves the aromatic character of the molecule and involves respectively 8 nickel surface atoms on the (100) face and 12 on the (111) face by adsorbed molecule. The interaction takes place via the π electrons of the ring. Significant shifts of the CHτ bending and CH stretching vibrations show a weakening of the CH bonds due to the formation of the chemisorption bond and a coupling of H atoms with the nickel substrate.     

Vibration spectroscopy of benzene adsorbed on Pt(111) and Ni(111)

High resolution electron energy loss spectroscopy has been applied to study the adsorption of benzene (C₆H₆ and C₆D₆) on Pt(111) and Ni(111) single crystal surfaces between 140 and 320 K. The vibrational spectra provide evidence that benzene is chemisorbed with its ring parallel to the surface, predominantly π bonded to the platinum and nickel surface respectively. A significant frequency increase of the CH-out-of-plane bending mode, largest in the case of platinum, is observed compared to the free molecule. On both metals two phases of benzene exist simultaneously, characterized by a different frequency shift. The shifts are explained by electronic interaction between the metal d-orbitals and molecules adsorbed in on top and threefold hollow sites respectively. The vibrational spectra of the multilayer condensed phase of benzene exhibit the infrared active modes of the gasphase molecule as expected.     

The chemistry of dimethyltetrazine on Pt(111)

As part of a program to further document the chemistry of CN on transition metal surfaces we have studied the decomposition of dimethyltetrazine on Pt(111). Products of the decomposition of dimethyltetrazine are H₂, N₂, HCN, C₂N₂ and small amounts of CH₃CN. Most of the methyl groups (>90%) are totally dehydrogenated leaving residual carbon on the surface. At low coverage the initial decomposition is CH bond cleavage. At higher coverage direct production of molecular N₂ at ~30°C is observed as the initial decomposition mode. Pretreatment of the Pt with H₂, shifts the high coverage decomposition to higher temperatures. Changes in the decomposition with coverage is explained as due to a change in bonding geometry. We suggest that at low coverage the molecular plane is parallel to the surface with the methyl groups in proximity to the surface, while at high coverage the molecule bonds on edge possibly through two adjacent nitrogens.     

A model calculation on adsorption of CO on the flat,stepped and kinked nickel surfaces

The adsorption of CO on Ni was investigated by quantum chemical calculations using the CNDO/2 tight binding method. The surfaces used as models are the (111), 4(111) × (111), 3(111) × (110) and 3(111) × (100) surfaces. The CO bond is weakened in this sequence of surfaces. The active sites for the CO bond fission are the trench regions of the step and kink structures. The Ni 3d orbitals play an important role for the weakening of the CO bond, though their contribution is small for the Ni-C bond formation.     

LEED,AES and thermal desorption studies of chemisorbed Hydrogen and hydrocarbons (C2H2, C2H4, C6H6, C6H12) on the (111) and stepped [6(111) × (100)] iridium crystal surfaces; comparison with platinum

The adsorption of hydrogen, ethylene, acetylene, cyclohexane and benzene was studied on both the (111) and stepped [6(111) × (100)] crystal surfaces of iridium. The techniques used were low energy electron diffraction, Auger electron spectroscopy, and thermal desorption mass spectrometry. At 30°C, acetylene, ethylene and benzene are adsorbed with a sticking probability near unity. The sticking probability of cyclohexane is less than 0.1 on both surfaces. Heating the (111) surface above 800°C, in the presence of the hydrocarbons, results in the formation of an ordered carbonaceous overlayer with a diffraction pattern corresponding to a (9 × 9) surface structure. No indication for ordering of the carbonaceous residue was found on the stepped iridium surface in these experimental conditions. The hydrocarbon molecules form only poorly ordered surface structures on both iridium surfaces when the adsorption is carried out at 30°C. Benzene is the only gas that can be desorbed from the surfaces in large amounts by heating. Ethylene remains largely on the surface, only a few percent is removed by heating while acetylene and cyclohexane cannot be desorbed at all. When adsorption is carried out at 30°C and the crystal is subsequently flashed to high temperature, hydrogen is liberated from the surface. The hydrogen desorption spectra from the iridium surfaces exposed to C₂H₄, C₂H₂, or C₆H₆ exhibit two hydrogen desorption peaks, one around 200°C and the second around 350°C. The temperatures where these peaks appear vary slightly with the type of hydrocarbon. The relative intensities of these two peaks depend strongly on the surface used. Arguments are presented that decomposition of the hydrocarbon molecules (C-H bond breaking nd possibly also C-C bond breaking) occurs easier on the stepped iridium surface than on the (111) surface. Hydrogen is desorbed at a higher temperature from an iridium surface possessing a high density of surface imperfections than from a perfect iridium (111) surface. The results are compared with those obtained previously on similar crystal surfaces of platinum. It appears that C-H bond breaking occurs more easily on iridium than on platinum.     

LCGTO-Xα model cluster study for the chemisorption of CO on twofold sites of Ni surfaces

The cluster Ni₂CO is studied as a simplified model for the chemisorption of CO on twofold bridging sites of transition metal surfaces. Using the LCGTO-Xα method we have calculated the potential energy surface for the totally symmetric stretching motion keeping the NiNi distance fixed at the bulk value. The minimum energy is found at a NiC distance of 1.72 Å and a CO bond length of 1.19 Å. The vibrational frequency for the CO bond (1850 cm^?1) shows reasonable agreement with EELS data (1810, 1870 cm^?1), whereas the (Ni₂)C frequency of 495 cm^?1 is remarkably higher than the experimental values (380, 400 cm^?1) indicating an overestimation of the chemisorption bond strength in this simple cluster model. The bonding between CO and Ni is analyzed using orbital correlations, ionization energies and Mulliken population analysis. Important bonding contributions from π backdonation are identified while the a₁orbital manifold exhibits strong antibonding effects.     

EELS analysis of the low temperature phase of ethylene chemisorbed on Pd(111)

The chemisorption of C₂H₄ and C₂D₄ on Pd(111) at 150 K has been studied by high resolution electron energy loss spectroscopy. Analysis of the vibrational spectra indicates that (i) C₂H₄ is more weakly bound on Pd(111) than on Ni(111) and Pt(111) and (ii) softened and broadened CH stretching frequencies suggest hydrogen bond-like interactions between the molecule and the metal surface.     

Vibrational spectra of ethylene and acetylene on metal surfaces - an electron energy loss study of ethylene adsorbed on Ni(110) and its carbided surface,and the use of metal-cluster analogies

An analysis has been made of on- and off-specular electron energy loss spectra (EELS) from C₂H₄ and C₂D₄ adsorbed on a clean Ni(110) and also a carbided Ni(110) surface. The carbided surface was prepared by heating the clean Ni surface in ethylene to 573 K or above. EELS spectra were obtained using a Leybold-Heraeus spectrometer at a beam energy of 3.0 eV and with a resolution of ca. 6.5 meV (ca. 50 cm^?1).The loss spectrum from ethylene at low temperatures (110 K) showed principal features at 3000 (w), 1468 (w), 1162 (s), 879 (w) and 403 cm^?1 (s) (C₂D₄ adsorption) and 2186 (w), 1258 (ms), 944 (ms), 645 (w) and 400 cm^?1 (s) (C₂D₄ adsorption). The overall pattern of wavenumbers and intensifies of the C₂H₄/C₂D₄ loss peaks is very similar in form (although systematically different in positions) to those previously observed on Ni(111) (ref.1) and Pt(111) (ref.2) surfaces at low temperatures. Like these earlier spectra,the EELS results for C₂H₄/C₂D₄ adsorbed on clean Ni(110) can be well interpreted in terms of a MCH₂CH₂M/MCD₂CD₂M species (M = metal) with the CC bond parallel to the surface.After adsorption on the carbided Ni(110) surfaces at 125 K,the main loss features occur at 3065 (m), 2992 (m), 1524 (ms), 1250 (s), 895 (s), and 314 cm^?1 (vs) (C₂H₄ adsorption) and 2339 (m), 2242 (m), 1395 (s), 968 (s), 661 (m) and 314 cm^?1 (vs). With the exceptions of reduced intensities of the bands at 895 cm^?1 (C₂H₄) and 661 cm^?1 (C₂D₄) this pattern of losses - particularly the 1550-1200 cm^?1 features which can be assigned to coupled νCC and δCH₂/δCD₂ modes - is well related to similar results on Cu(100) (ref.3) and Pd(111) (ref.4) which have been interpreted convincingly in terms of the presence of π-bonded species, (C₂H₄)M or (C₂D₄)M on the surface. This structural assignment is supported by comparison with the vibrational spectra of Zeise's salt, K[PtCl₃(C₂H₄)].H₂O (refs.5&6).Spectral changes occur on warming C₂H₄ on the clean Ni(110) surface with a growth of a feature near 895 cm^?1 at 200 K. At 300 K a rather poorly-defined spectrum occurs, which differs substantially from those found on (111) surfaces of Pt (ref.2), Rh (ref.7) or Pd (ref.8) at room temperature. These latter have been attributed to the ethylidyne, CH₃.CM₃, surface species (ref.9). For adsorption on Ni(110) there is clearly a mixture of species at room temperature.The analysis of the vibrational spectra of selected metal-cluster compounds of known structure with selected hydrocarbon ligands has helped substantially to assign the spectra of surface species in terms of bonding structures of the adsorbed species, as in the cases of the identification of (C₂H₄)M π-adsorbed (refs.5&6) and the ethylidyne CH₃.CM₃ species (ref.9). We have recently analysed the infrared and Raman spectra of the cluster compound (C₂H₂)Os₃(CO)₁₀ and its deuterium-containing analogue. The infrared frequency and intensity pattern for the A′ modes (C_S symmetry) of the two isotopomers bears a remarkable resemblance to EELS spectra previously obtained at low temperature for C₂H₂/C₂D₂ adsorbed on Pt(111) (ref.2) and (after taking into account systematic frequency shifts) for Pd(111) (ref.4). There is good evidence for believing that the structure of the hydrocarbon ligand interacting with the osmium complex takes the form

where the arrow denotes a π-bond to the third metal atom. This strongly confirms the structure for the low-temperature acetylene species on Pt(111) as proposed by Ibach and Lehwald (ref.2).Finally the room-temperature spectra for ethylene adsorbed on finely-divided silica-supported Pt and Pd catalysts have previously been interpreted in terms of the presence of MCH₂CH₂M (ref.10) and π-bonded (C₂H₄)M species (ref.11). However comparisons with the more recent EELS spectra from ethylene on Pt(111) at room temperature (ref.2) now leads to a reassignment of the 2880 cm^?1 band, on Pt, previously assigned to MCH₂CH₂M, together with a new, related,band at 1340 cm^?1 (ref.12), to the ethylidyne species CH₃CPt₃ found on the single crystal surface.More detailed analyses of the spectra reported here will be published later. Acknowledgement is given to substantial assistance for this programme of research from the Science and Engineering Research Council.     

Penning ionization electron spectroscopy of molecular adsorbates on Pd and Cu surfaces

The electronic properties of CO, PF₃, NH₃, C₂H₂ and C₆H₆ adsorbed on Pd(111), Pd(110), and Cu(110) surfaces were studied by Auger deexcitation (AD) of metastable noble gas atoms (Penning ionization) and by ultraviolet photoelectron spectroscopy (UPS). Electron emission via AD is restricted to the outmost levels localized at the adsorbed particles. The AD process competes with reasonance ionization of the metastable atoms, and its probability depends on the geometry of the adsorbed species and on its adsorption sites as well as on coverage. The differences in kinetic energy of electrons emitted by AD or by photons reflect modifications of the electron affinities of the adsorbed molecules. The extreme surface sensitivity of AD spectroscopy allows in particular to probe the local density of states at the adsorbate in the energy range close to the Fermi level which arises from π “back donation” as well as σ antibonding contributions.     

Bonding of C2H4 to Cu-, Ag- and Au- “SERS-active” films

The πσ-parameter (defined such, that di-σ-bonding corresponds to one) is 0.12, 0.26 and 0.29 for C₂H₄ adsorbed at “SERS-active sites” on coldly deposited Ag-, Cu- and Au-films. There is a qualitative correspondence to the respective desorption temperatures. The evaluated πσ-parameters are nearly identical to those for adsorption on single crystalline noble metal surfaces and cationic C₂H₄-noble metal complexes, but definitely different from πσ-parameters of neutral C₂H₄-noble metal complexes.     

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.     

EFFECT OF ATOMIC HYDROGEN ON THE ACETYLENE-ADSORBED Si(100)(2×1) SURFACE AT ROOM TEMPERATURE

High resolution electron energy loss spectroscopy, low energy electron diffraction and quadrupole maas spectrometer (QMS) have been employed to study the effect of atomic hydrogen on the acetylene-saturated pre-adsorbed Si(100)(2×1) surface and the surface phase transition at room temperature. It is evident that the atomic hydrogen has a strong effect on the adsorbed C₂H₂ and the underlying surface structure of Si. The experimental results show that CH and CH₂ radicals co-exist on the Si surface after the dosing of atomic hydrogen; meanwhile, the surface structure changes from Si(100)(2×1) to a dominant of (1×1). These results indicate that the atomic hydrogen can open C=C double bonds and change them into C-C single bonds, transfer the adsorbed C₂H₂ to C₂H_x(x = 3,4) and break the underlying Si-Si dimer, but it cannot break the C-C bond intensively. The QMS results show that some C₄ species axe formed during the dosing of atomic hydrogen. It may be the result of atomic hydrogen abstraction from C₂H_x which leads to carbon catenation between two adjacent C-C directs. The C₄ species formed are stable on Si(100) surfaces up to 1100 K, and can be regarded as the potential host of diamond nucleation.     

Phenolic polymer–surface interactions from ab initio computations

Test calculations show that the diamond surface binding energy of C₁₃H₁₁O₂, the simplest model for phenolic, is virtually the same as that of C₆H₅. Using the C₆H₅ model, we compare the binding to a diamond surface, a graphene sheet, a (10, 0) nanotube, and a silica surface. The binding energy is more than 5?eV for the silica and 2.85?eV for the diamond surface. As expected, the binding energy of a second molecule at a site adjacent to the first molecule is larger than the first binding energy for the graphene sheet and the carbon nanotube, since the first C₆H₅ bond breaks a π bond and the second molecule bonds to the unpaired π electron created by adding the first molecule. For all of the systems, adding a C₂ unit between the surface and the C₆H₅ group increases the binding by at least 0.51?eV and up to 2.3?eV. Part of this increase is due to the intrinsically stronger bonding for the sp hybridization and part due to a decrease in the surface–C₆H₅ repulsion.     

c-C5H5 on a Ni(1 1 1) surface: Theoretical study of the adsorption, electronic structure and bonding

In the present work the ASED-MO method is applied to study the adsorption of cyclopentadienyl anion on a Ni(1 1 1) surface. The adsorption with the centre of the aromatic ring placed above the hollow position has been identified to be energetically the most favourable. The aromatic ring remains almost flat, the H atoms are tilted 17° away from the metal surface. We modelled the metal surface by a two-dimensional slab of finite thickness, with an overlayer of c-C₅H₅⁻, one c-C₅H₅⁻ per nine surface Ni atoms. The c-C₅H₅⁻ molecule is attached to the surface with its five C atoms bonding mainly with three Ni atoms. The NiNi bond in the underlying surface and the CC bonds of c-C₅H₅⁻ are weakened upon adsorption. We found that the band of Ni 5dz² orbitals plays an important role in the bonding between c-C₅H₅⁻ and the surface, as do the Ni 6s and 6p_z bands.     

Experimental study of the vibrations of acetylene chemisorbed on Ni(111)

High resolution electron energy-loss measurements of normal and deuterated acetylene chemisorbed on Ni(111) have been obtained. Observed vibrational modes are identified using the frequency shifts for the deuterated species and comparisons to the free molecule and a di-cobalt compound of acetylene. These vibrational frequencies indicate that chemisorbed acetylene is strongly rehybridized having a state of hybridization between ~sp^2.5 and sp³. Consideration of the types of modes observed, their assignments and the surface selection rule suggests a molecular orientation with the C-C bond axis slightly skewed relative to the surface and with the plane of the distorted molecule normal to the surface. A bonding geometry is proposed which has the carbon atoms residing above two adjacent 3 fold hollow sites of the Ni surface. This molecular geometry differs from that deduced previously by electron energy-loss spectroscopy for molecularly adsorbed acetylene on Pt(111).     

Characterization of aromatic-thiol π-type hydrogen bonding and phenylalanine-cysteine side chain interactions through ab initio calculations and protein database analyses

In this study, the aromatic-thiol π hydrogen bonding and phenylalanine-cysteine side chain interactions are characterized through both molecular orbital calculations on a C₆H₆-HSCH₃ model complex and database analyses of 609 X-ray protein structures. The aromatic-thiol π hydrogen bonding interaction can achieve a stabilization energy of 2.60 kcal mol^?1, and is stronger than the already documented aromatic-hydroxyl and aromatic-amino hydrogen bonds. However, the occurrence of the aromatic-thiol hydrogen bond is rather rare in proteins. This is because most of the thiol groups participate in the formation of either disulphide bonds or stronger S—H…O (or N) ‘normal’ hydrogen bonds in a protein environment. Interactions between the side chains of phenylalanine and cysteine residues are characterized as the phenyl(Phe)(HSCH₂-)(Cys) interaction. The bonding energy for such interactions is approximately 3.71 kcal mol-¹ and is achieved in a geometric arrangement with an optimal phenyl(Phe)-(HS-)(Cys) π-type hydrogen bonding interaction. The interaction is very sensitive to the orientation of the two lone electron pairs on the sulphur atom relative to the π electron cloud of the phenyl ring. Accordingly, the interaction configurations that can accomplish a significant bonding energy exist only within a narrow configurational space. The database analysis of 609 experimental X-ray protein structures demonstrates that only 268 of the 1620 cysteine residues involve such phenylalanine-cysteine side chain interactions. Most of these interactions occur in the form of π (aromatic)-lone pair(sulphur) attractions, and correspond to a bonding energy less than 1.5 kcal mol^?1. A few were identified as the aromatic-thiol hydrogen bond with a bonding energy of 2.0–3.6 kcal mol^?1.     

Adsorption behavior of H2O on clean and oxygen precovered Ni(s)(111)

Photoelectron spectroscopy (UPS), thermal desorption spectroscopy (TDS), isotope exchange experiments, work function change (δφ) and LEED were used to study the adsorption and dissociation behavior of H₂O on a clean and oxygen precovered stepped Ni(s)[12(111) × (111)] surface. On the clean Ni(111) terraces fractional monolayers of H₂O are adsorbed weakly in a single adsorption state with a desorption peak temperature of 180 K, just above that of the ice multilayer desorption peak (T_m = 155 K). In the angular resolved UPS spectra three H₂O induced emission maxima at 6.2, 8.5 and 12.3 eV below E_F were found for θ ≈ 0.5. Angular and polarization dependent UPS measurements show that the C_2v symmetry of the H₂O gas-phase molecule is not conserved for H₂O(ad) on Ni(s)(111). Although the Δφ suggest a bonding of H₂O to Ni via the negative end of the H₂O dipole, the O atom, no hints for a preferred orientation of the H₂O molecular axes were found in the UPS, neither for the existence of water dimers nor for a long range ordered H₂O bilayer. These results give evidence that the molecular H₂O axis is more or less inclined with respect to the surface normal with an azimuthally random distribution. H₂O adsorption at step sites of the Ni(s)(111) surface leads in TDS to a desorption maximum at T_m = 225 K; the binding energy of H₂O to Ni is enhanced by about 30% compared to H₂O adsorbed on the terraces. Oxygen precoverage causes a significant increase of the H₂O desorption energy from the Ni(111) terraces by about 50%, suggesting a strong interaction between H₂O and O(ad). Work function measurements for H₂O+O demonstrate an increase of the effective H₂O dipole moment which suggests a reorientation of the H₂O dipole in the presence of O(ad), from inclined to a more perpendicular position. Although TDS and Δφ suggest a significant lateral interaction between H₂O+O(ad), no changes in the molecular binding energies in UPS and no “isotope exchange” between ¹⁸O(ad) and H₂¹⁶O(ad) could be observed. Also, dissociation of H₂O could neither be detected on the oxygen precovered Ni(s)(111) nor on the clean terraces.