Reflection-absorption infrared spectroscopy of adsorbates on a Cu(111) single crystal surface

A Fourier Transform infrared spectrometer has been attached to an ultrahigh vacuum (UHV) apparatus in order to perform reflection-absorption infrared Spectroscopy (RAIRS) of adsorbed species on well-defined surfaces.An infrared spectrum of carbon monoxide (CO) adsorbed at 90 K on Cu(111) has been measured using a resolution of 2 cm⁻¹ and a measuring time of 60 s. Coverages below 1 % of a monolayer are easily detectable.Tetracyanoethylene (TCNE) has been adsorbed at various coverages at 100 K on Cu(111). Strongly red-shifted CN stretchings modes due to charged TCNE adspecies are observed at low coverage. The RAIRS spectrum of the condensed phase is characteristic of crystalline TCNE.Finally, isotopically labeled ¹²C and ¹³C acetonitrile (CH₃CN) has been adsorbed on Cu(111) as multilayers. Shifts caused by isotopic labeling as small as 3 cm⁻¹ are easily detected.     

Electronic excitation of ice monomers on Au(111) by scanning tunneling microscopy

Scanning tunneling microscopy, inelastic tunneling spectroscopy, and electron induced manipulation are used to investigate electronic excitation of D₂O monomers and small clusters adsorbed at the elbows of the Au(111) reconstruction. Diffusion of molecules, dissociation of clusters, and rearrangement of the reconstruction is induced by electronic excitation. Threshold energies of between 200 and 250 meV and of 446 meV are explained by combined vibrational modes of D₂O molecules. External vibrational modes of D₂O molecules on Au(111) are identified by inelastic tunneling spectroscopy at ≈18, 30, and 41 meV.     

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.     

Low energy adsorbate vibrational modes observed with inelastic helium atom scattering: CO on Pt(111)

We report on new low energy loss and gain features which appear in the time-of-flight distributions of He atoms scattered from CO adsorbed on Pt(111). On the basis of calculated normal mode energies we assign the 6 meV features to the excitation of the CO vibrational mode corresponding to a hindered translation of the upright molecule parallel to the surface. The energy and intensity of the 6 meV mode as a function of coverage, sample temperature and scattering conditions are investigated. At high coverages, concurrent with the appearance of a well ordered (4 × 2) overlayer structure, the 6 meV mode is observed to broaden and shift in energy to about 7.4 meV. The dispersion curve measured at high coverages is flat suggesting that there is no direct coupling between hindered translations of adjacent CO molecules.     

Adsorption sites of CO on Pt (111)

The surface vibrations of CO adsorbed on Pt(111) single crystal surfaces at 320 K have been studied by electron-energy-loss spectroscopy. At low coverages two vibration modes at 58 and ∼260 meV are observed. For exposures >0.2 Langmuir two additional modes at 45 and 232 meV develop. Considering also the observed LEED structures these vibrations are attributed to CO molecules being adsorbed upright in on-top and bridge sites, respectively.     

Helium scattering and work function investigation of co adsorption on Pt(111) and vicinal surfaces

CO adsorption on Pt(111) and vicinal Pt(111) surfaces has been studied by means of work function variation and He scattering measurements. AES and LEED were used mainly for correlations with other work. Special attention has been paid to the low coverage regime (θ_co < 0.1) with emphasis on surface structural dependencies. The minimum of the work function versus CO exposure curve occurs at a coverage less than 11% on “kink-free” surfaces. This is much lower than the hitherto commonly accepted value of 33%, and does not relate to any observed LEED superstructure. The value of Δφ_min depends strongly on the surface structure. For an “ideal” Pt(111) surface with a step density less than 10^?3 at a temperature of 300 K, Δφ_min = ?240 meV. The scattering cross section Σ of CO adsorbed on Pt(111) for 63 meV He is typically > 250 Ų, i.e. much larger than expected from the Van der Waals radii of He and CO. For two nominal Pt(111) surfaces with step densities of 10^?2 and less than 10^?3, respectively, the measured Σ values varied by a factor of three. This can be explained by preferential CO occupation of defect sites, which are already not “seen” by thermal helium. By comparing results on a stepped (997) and a kinked (12 11 9) Pt surface with similar defect densities, the kinks are proven to play a decisive role. They probably form saddles in the recently proposed activation barrier for migration between terrace and step sites.     

Comparison between the adsorption properties of Pd(111) and PdCu(111) surfaces for carbon monoxide and hydrogen

Thermal desorption spectroscopy and LEED have been used to investigate the interaction of CO and hydrogen with a Pd_0.75Cu_0.25(111) single crystal surface with surface composition of about Pd_0.7Cu_0.3. The main objective was to make a comparison with the previously studied Pd_0.67Ag_0.33(111) (surface composition Pd_0.1Ag_0.9) and Pd(111) surfaces. In addition, the effect of preadsorbed H on subsequent CO dosage and the effect of adsorbed CO on postdosed hydrogen are described. Marked differences were found in the adsorption behaviour of the three surfaces towards CO and hydrogen. The maximum amount of H and CO that can be adsorbed at 250 K and pressures below 10⁻⁹ mbar is much lower on the PdCu surface than expected on the basis of the surface composition. This effect appears to be caused by a low heat of adsorption of hydrogen and CO and Pd singlet sites. Arguments are presented that singlet Pd sites or isolated Pd atoms in a Cu or Ag matrix are able to trap and dissociate the hydrogen molecule at 250 K. The CO desorption spectra are not influenced by pre- or postexposed hydrogen. Adsorbed CO hampers the uptake of hydrogen upon subsequent exposure to hydrogen. Postdosed CO causes adsorbed H adatoms to move to the bulk (adsorbed H). CO exposure at 250 K results in a very broad desorption plateau between 310 and 425 K with hardly discernable maxima. The results can be explained in terms of the size and relative concentration of the various Pd sites present on the surface (triplet, doublet and singlet sites). It can be concluded that for Pd (111) the heat of adsorption of both CO and H differ appreciably for the triplet, doublet and singlet sites. The effect of site has a larger contribution to the decrease of the heat of adsorption with coverage than the effect of lateral interaction in the adlayer. For Pd(111), PdCu(111) and PdAg(111) the effect of the available Pd sites is the major effect that determines the heat of adsorption, followed by the effect of lateral interaction and for the alloy surfaces the electronic or ligand effect.     

Surface chemistry of polyimide precursors on Cu(111)

We have investigated the bonding of the monomers pyromellitic dianhydride (PMDA) and oxydianiline (ODA) as well as model compounds, succinic anhydride, phthalic anhydride, and benzoic acid, on Cu(111) in ultrahigh vacuum. Unenhanced surface Raman spectroscopy was used to identify the adsorbed species. ODA was unreactive at 110 K; the surface vibrational features were identical to those in the condensed multilayer. In contrast, PMDA chemisorbed dissociatively to form a bidentate surface carboxylate. Succinic anhydride physisorbed at 110 K, whereas benzoic acid and phthalic anhydride both adsorbed dissociatively forming bridging surface carboxylates as was observed for PMDA. The surface Raman spectrum of PMDA showed resonance enhancement.     

The adsorption of ethylene oxide on Ag(110) and Pt(111): Relevance to selective olefin oxidation

The interactions of ethylene oxide (EtO) with the Ag(110) and Pt(111) surfaces have been studied using XPS, TDS, AES and EELS. On Ag(110), the interaction is very weak, with only molecular desorption observable. The heat of adsorption is ≈ 10.1 kcal mole⁻¹. In contrast, decomposition reactions strongly predominate on Pt(111) at low coverage. Molecular desorption is only seen at high coverages. The heat of adsorption decreases from > 11.9 to 10 kcal mole⁻¹ with increasing coverage. Condensed multilayers desorb at ≈ 140 K. Ultimate decomposition products on Pt(111) include H₂ and CO gas, and carbon residue on the surface. Evidence suggests that adsorbed decomposition intermediates may include atomic hydrogen, CO, acetyl and ethylidyne species, with at least one other, yet unidentified, species. These results imply that, if produced, adsorbed ethylene oxide would be unlikely to escape a reactor containing Pt catalyst without further decomposition reactions. This may help explain the uniqueness of Ag catalysts in ethylene epoxidation.     

Electronic excitations on clean and adsorbate-covered oxide surfaces

We have studied electronic excitations at the surfaces of NiO (100), Cr₂O₃(111), and Al₂O₃(111) thin films with Electron Energy Loss Spectroscopy (EELS). On NiO (100) we observe surface electronic excitations in the energy range of the band gap which shift upon adsorption of NO. Ab initio cluster calculations show that these excitations occur within the Ni ions at the oxide surface. The (111) surface of Cr₂O₃ is characterized by distinct excitations which are also strongly influenced by the interaction with adsorbates. Temperature-dependent measurements show that two different states of the surface exist which are separated by an activation energy of about 10 meV. For Al₂O₃(111) we present data for a CO adsorbate. The oxide is quite inert with respect to CO adsorption as indicated by desorption temperatures between 38 K and 67 K. Due to the weak interaction with the substrate the a³II valence excitation of CO shows a clearly detectable vibrational splitting which has not been observed previously for a CO adsorbate in the (sub)monolayer coverage range. For several different adsorption state the lifetimes of the a³II state could be estimated from the halfwidths of the loss peaks, yielding values between 10^–15 s for the most strongly bound species and 10^–14 s for the CO multilayer.     

CO adsorption on Ni(1 0 0): Evidences for a weakly bound phase by HREELS measurements

The vibrational properties of CO on Ni(1 0 0) were investigated by high resolution electron energy loss spectroscopy. Loss measurements were performed as a function of temperature and CO exposures. At room temperature, regardless of CO coverage, we found stretching energies at 250 meV and 240 meV, assigned to CO at atop and bridge sites, respectively. At low temperature and for CO exposures lower than 0.6 L, the loss spectra showed a single stretching peak at 240 meV which is assigned to CO at bridge sites. For higher doses, a new intense peak at 260 meV appeared in the loss spectra. The rise of this new loss strongly influenced the intensity of the peak at 240 meV suggesting the occurrence of dipole couplings between adjacent CO molecules. This unusual high stretching frequency leads us to assign the peak at 260 meV to the stretching vibration of CO molecules which are weakly bonded to the Ni surface. We suggest that the formation of this phase is due to an electronic effect arising from a reduced back donation of electrons into the empty π orbital of CO.     

Energetics and vibrational states for hydrogen on Pt(111)

We present a combination of theoretical calculations and experiments for the low-lying vibrational excitations of H and D atoms adsorbed on the Pt(111) surface. The vibrational band states are calculated based on the full three-dimensional adiabatic potential energy surface obtained from first-principles calculations. For coverages less than three quarters of a monolayer, the observed experimental high-resolution electron peaks at 31 and 68 meV are in excellent agreement with the theoretical transitions between selected bands. Our results convincingly demonstrate the need to go beyond the local harmonic oscillator picture to understand the dynamics of this system.     

Atomic and molecular adsorption on Pd(111)

The adsorption properties of a variety of atomic species (H, O, N, S, and C), molecular species (N₂, HCN, CO, NO, and NH₃) and molecular fragments (CN, NH₂, NH, CH₃, CH₂, CH, HNO, NOH, and OH) are calculated on the (111) facet of palladium using periodic self-consistent density functional theory (DFT–GGA) calculations at ¼ ML coverage. For each species, we determine the optimal binding geometry and corresponding binding energy. The vibrational frequencies of these adsorbed species are calculated and are found to be in good agreement with experimental values that have been reported in literature. From the binding energies, we calculate potential energy surfaces for the decomposition of NO, CO, N₂, NH₃, and CH₄ on Pd(111), showing that only the decomposition of NO is thermochemically preferred to its molecular desorption.     

Photoemission from physisorbed Co on clean and Xe-covered Al(111)

Molecular-orbital energy shifts are observed in photoemission from weakly physisorbed CO on clean and Xe-covered Al(111) surfaces. These shifts in ionization potentials are mainly due to final-state relaxation effects, which can be described approximately by a point-charge image-potential model. Differential distance- and orbital-dependent energy shifts suggest that CO molecules lie flat on the substrates. CO is adsorbed on Al(111) with a heat of formation of 0.21 eV/molecule.     

The adsorption of N2: Chemisorbed on Ni(110) and physisorbed on Pd(111)

The bonding of molecular N₂ has been investigated with angle resolved photoelectron spectroscopy and inelastic electron scattering. The spectra obtained from N₂ chemisorbed onto a Ni(110) surface are compared to CO chemisorbed onto Ni(110) and to N₂ physisorbed onto Pd(111). The N₂ molecular axis was found to be normal to the crystal surface for the chemisorbed state on Ni(110) and random for the physisorbed state on Pd(111). The NN and NiN₂ stretching frequecies indicate that the N₂ molecule is terminally bonded to a single Ni atom on Ni(110). The binding energies of the two outer σ states and one π state of chemisorbed N₂ were measured, indicating that the bonding of N₂ to a metal surface is different than CO. Both σ states drop in energy compared to the π level due to the fact that both of them are involved in the N₂ substrate bond. The symmetry of the gas phase N₂ molecule is reduced upon adsorption. The consequences of this are seen in the dipole active NN vibrational mode, the large intensity of the Ni-N₂ vibrational mode and the coupling of the adsorbate 4σ(2σ_u) level to the final state resonance which is forbidden by symmetry in the gas phase. Many electron excitation satellite lines are observed in the valence spectra of both the chemisorbed and physisorbed N₂. The physisorbed satellite lines are nearly identical to those seen in gas phase N₂, while the chemisorbed N₂ spectra has new satellite structure, due to the interaction with the substrate.     

Mo(CO)6在清洁的和氧化的Si(111)表面上吸附的对比

采用高分辨电子能量损失谱对比研究Mo(CO)₆在清洁的、预吸附氧的和深度氧化的Si(111)表面上的吸附行为. 吸附Mo(CO)₆的C-O伸缩振动模式向低频方向移动,说明Mo(CO)₆与清洁Si(111)和SiO₂/Si(111)表面发生了不同的相互作用,前者较弱而后者较强. 与SiO₂/Si(111)表面的强相互作用可能引起Mo(CO)₆部分解离,形成部分分解的羰基钼物种.     

Valence and core excitations in rare gas mono- and multilayers: Production,decay, and desorption of neutrals and ions

The aim of this survey is the understanding of the dynamics of medium to high energy excitations in simple condensed systems on very short time scales. For this purpose we examine the modifications of the electronic excitations and their evolution in rare gases (mainly Ar and Kr) due to a nearby metal surface (monolayer case) or by embedding into a rare gas condensate (multilayers). Ionic excitations are shifted to lower energies compared to the gas phase by polarization of the surroundings, while neutral excitations stay constant or are shifted to somewhat higher energies. This decreases the spacing between excitonic and ionic states from both sides. Deexcitation events can be analysed by linewidths for valence excitations, and by comparison of autoionisation and Auger spectra for core excitations. For monolayers, we conclude that excitonic states are unstable relative to ionic states but nevertheless are quite long-lived. For multilayers, only minor modifications relative to the gas phase are usually found. All electronic excitations in Ar and Kr mono- or multilayers lead to desorption of neutrals; core excitations in multilayers also lead to ions and cluster ions. The probable mechanisms in all cases are discussed, and open questions are pointed out.     

Co stretching vibration of carbon monoxide adsorbed on nickel(111) studied by high resolution electron loss spectroscopy

The frequency of the v-CO stretching vibration measured by HRELS has been followed as a function of the CO coverage and in the presence of coadsorbed hydrocarbons on the Ni(111) face. The v-CO frequency shifts continuously from 225 meV (1814 cm^?1) to 237 meV (1911 cm^?1) when the CO coverage increases from 0 to 0.41. Coadsorption of electron donor molecules, such as ethylene and benzene, generates a significant lowering of the v-CO frequency. Results are discussed in terms of the back donation of metallic electrons into the 2π ¹ antibonding orbitals of CO, the dipole-dipole coupling and the coordination number of the CO adsorbed molecules. The back donation is found to play the major role in the range of coverage explored but we cannot exclude some contribution of a dipole-dipole coupling effect.     

Interactions between NO and CO on Pt(111)

Temperature programmed desorption (TPD) of coadsorbed NO and CO on Pt(111) shows that no reaction occurs (less than 2%) up to the desorption temperature of NO. At 100 K, adsorption is competitive, but neither gas displaces the other from the surface. Coadsorbed CO causes the NO desorption temperature to be lowered by as much as 100 K, but NO does not affect the CO desorption temperature. TPD spectra for NO depend on which gas is adsorbed first, indicating that equilibrium between species is not established on the surface during desorption. Electron energy loss spectra show that the vibrational spectrum of each gas is only weakly affected by the other. When NO is adsorbed first, CO does not affect the ratio of bridged and terminal NO but lowers the frequencies of the bridged NO by approximately 50 cm^?1 and lowers the intensities of vibrational peaks of both species by a factor of about four. When CO is adsorbed first, the ratio of terminal to bridged NO increases for given coverage of NO, and the frequency of the bridged NO remains at the pure NO value. These results are explained in terms of CO island formation, repulsive interactions between NO and CO, and low adsorbate mobilities.     

Methanol decomposition on platinum (111)

The interaction of methanol with clean and oxygen-covered Pt(111) surfaces has been examined with high resolution electron loss spectroscopy (EELS) and thermal desorption spectroscopy (TDS). On the clean Pt(111) surface, methanol dehydrogenated above 140 K to form adsorbed carbon monoxide and hydrogen. On a Pt(111)-p(2 × 2)O surface, methanol formed a methoxy species (CH₃O) and adsorbed water. The methoxy species was unstable above 170 K and decomposed to form adsorbed CO and hydrogen. Above room temperature, hydrogen and carbon monoxide desorbed near 360 and 470 K, respectively. The instability of methanol and methoxy groups on the Pt surface is in agreement with the dehydrogenation reaction observed on W, Ru, Pd and Ni surfaces at low pressures. This is in contrast with the higher stability of methoxy groups on silver and copper surfaces, where decomposition to formaldehyde and hydrogen occurs. The hypothesis is proposed that metals with low heats of adsorption of CO and H₂ (Ag, Cu) may selectively form formaldehyde via the methoxy intermediate, whereas other metals with high CO and H₂ chemisorption heats rapidly dehydrogenate methoxy species below room temperature.