Ultrafast laser excitation of CO/Pt(111) probed by sum frequency generation: coverage dependent desorption efficiency

CO photodesorption from Pt(111) induced by femtosecond laser pulses is probed by IR+visible sum frequency generation (SFG). Steady state analysis of SFG spectra at varying CO pressure and laser fluence allows one to measure a approximately 5 orders of magnitude decrease of the photodesorption rate constant when CO coverage decreases from 0.37 to 0.07 monolayer. We ascribe this effect in the framework of the Menzel-Gomer-Redhead mechanism to electron delocalization in the CO layer. The lifetime of electronic excitation decreases when coverage decreases.     

CO stretching vibrations on Pt(111) and Pt(110) studied by sumfrequency generation

Optical sum-frequency generation (SFG) is used to characterize CO stretching vibrations on Pt(111) and Pt(110) surfaces. Different adsorption sites (terminal, bridge and step sites) are identified in the SFG spectra of CO on Pt(111), in good quantitative agreement with previous infrared reflection-absorption experiments on this system. For CO on Pt(110) we only observe CO molecules on terminal sites. The measured CO stretching vibration frequencies on Pt(110), both for low and high coverages, are at variance with the results of previous infrared studies. Our SFG results for CO on Pt(110) are confirmed by independent EELS measurements which, in addition, also reveal the frustrated rotational mode and the metal-CO vibration. The measured frequency of 2065 cm⁻¹ for low CO coverage on Pt(110)-(1 × 2) is consistent with a previously proposed empirical relation between the frequency of an isolated adsorbed CO molecule and the coordination number of the binding Pt surface atom.     

Optical sum-frequency emission from langmuir-blodgett films of variable thickness: effects of the substrate and polar orientation of fatty acids in the films

The nonlinear optical response arising from a model multilayer structure, i.e., Langmuir-Blodgett (LB) films comprised of different numbers of per-protonated (H) and per-deuterated (D) fatty acid layers on solid substrates, has been evaluated by sum-frequency generation (SFG) spectroscopy. The SFG signals depend significantly on the absolute polar orientation of the fatty acids in the individual layers and on the nonlinear optical response of the substrate. The SFG spectra on gold and fused quartz substrates demonstrate a totally different dependence on the number of the contributing H layers, which it is possible to analyze quantitatively. The results provide important information for understanding the origin of the nonlinear optical responses from ordered systems composed of multiple interfaces and therefore for extracting exact structural information about each interface from the observed SFG signals.     

Sum frequency generation and density functional studies of CO-H interaction and hydrogen bulk dissolution on Pd(1 1 1)

CO-H interaction and H bulk dissolution on Pd(1 1 1) were studied by sum frequency generation (SFG) vibrational spectroscopy and density functional theory (DFT). The theoretical findings are particularly important to rationalize the experimentally observed mutual site blocking of CO and H and the effect of H dissolution on coadsorbate structures. Dissociative hydrogen adsorption on CO-precovered Pd(1 1 1) is impeded due to an activation barrier of ∼2.5 eV for a CO coverage of 0.75 ML, an effect which is maintained down to 0.33 ML CO. Preadsorbed hydrogen prevented CO adsorption at 100 K, while hydrogen was replaced from the surface by CO above 125 K. The temperature-dependent site blocking of hydrogen originates from the onset of hydrogen diffusion into the Pd bulk around 125 K, as shown by SFG and theoretical calculations using various approaches. When Pd(1 1 1) was exposed to 1:1 CO/H₂ mixtures at 100 K, on-top CO was absent in the SFG spectra although hydrogen occupies only threefold hollow sites on Pd(1 1 1). DFT attributes the absence of on-top CO to H atoms diffusing between hollow sites via bridge sites, thereby destabilizing neighboring on-top CO molecules. According to the calculations, the stretching frequency of bridge-bonded CO with a neighboring bridge-bonded hydrogen atom is redshifted by 16 cm⁻¹ when compared to bridging CO on the clean surface. Implications of the observed effects on hydrogenation reactions are discussed and compared to the C₂H₄-H coadsorption system.     

Sum-frequency generation and temperature-programed desorption studies of formic acid on MgO(001) surfaces

Adsorption and decomposition of formic acid on MgO(001) surfaces were studied by means of Sum-Frequency Generation (SFG), Temperature-Programed Desorption (TPD) and Atomic Force Microscopy (AFM). Formic acid was dissociatively adsorbed on MgO(001) surfaces at room temperature. From SFG and TPD measurements, the existence of several different types of formate species was deduced and all species mainly decomposed into CO and H₂O on raising the temperature of the substrate.Paper presented at the 129th WE-Heraeus-Seminar on Surface Studies by Nonlinear Laser Spectroscopies, Kassel, Germany, May 30 to June 1, 1994     

Samarium atom yield under electron-stimulated desorption from oxidized tungsten surface

The yield of samarium (Sm) atoms under electron stimulated desorption from Sm layers adsorbed on the surface of oxidized tungsten was studied as a function of incident electron energy, surface coverage by samarium, degree of tungsten oxidation, and substrate temperature. The measurements were conducted by the time-of-flight technique with a surface ionization detector in the substrate temperature interval from 140 to 600 K. The yield vs. incident electron energy function has a resonance character. Overlapping resonance peaks of Sm atoms are observed at electron energies of 34 and 46 eV, which may be related to excitation of the Sm 5p and 5s levels. The Sm yield is a complex function of samarium coverage and substrate temperature. Sm atom peaks occur only in the Sm coverage range from 0 to 0.2 monolayers (ML), in which the yield passes through a maximum. The shape of the yield temperature dependence is a function of Sm coverage. For low Sm cover-ages (<0.07 ML), the yield decreases slowly with the temperature increasing to 270 K, after which it drops to zero at temperatures above 360 K. At higher coverages, the Sm yield passes through a maximum with increasing temperature and additional peaks appear at electron energies of 42, 54, and 84 eV, which can be assigned to excitation of the tungsten 5p and 5s levels. These peaks are most likely associated with desorption of SmO molecules, whose yield reaches a maximum at an Sm coverage of about 1 ML.     

Adsorption of CO on Ni-promoted TiO2(110)

The valence-band structure and the vibrational modes of CO adsorbed on nickel-promoted TiO₂(110) surfaces as a function of CO exposure have been studied by means of ultraviolet photoelectron spectroscopy (UPS) and high-resolution electron energy-loss spectroscopy (HREELS). It is found that CO exists in molecular form at room temperature on the nickel-promoted TiO₂(110) surfaces and most likely binds to the Ni atoms or nickel-affected sites rather than to the substrate atoms. At saturation coverage, CO molecules adsorb simultaneously on the 2-fold bridge sites and terminal sites on the (111)-oriented Ni islands deposited upon TiO₂(110). The occupation of the edge sites of Ni islands gives rise to an anomalously low frequency of the C---O stretching vibration. This frequency, indicative of a weakened C---O bond, suggests existence of a precursor to the dissociated state.     

Mercury induced reorientation of alkanethiolates adsorbed on gold

3 -(CH₂)₂₁-SH) were investigated by IR-vis sum frequency generation (SFG). Well-ordered monolayers and films with submonolayer coverage with a high number of gauche conformations were prepared on polycrystalline gold substrates. Exposure to a saturated mercury atmosphere induces a major reorganization of the adsorbate phase indicated by a decrease of the average cant angle. Additionally, well-ordered films show an increase of gauche defects upon amalgamation. In contrast, films with submonolayer coverage exhibit an improvement of molecular order. The experiments suggest that amalgamation flattens the corrugation potential of the substrate and yields a separation of the thiol layer into areas of low thiol density with highly disordered alkyl chains and of higher density than on gold with an orientation of the molecules similar to what is observed on silver substrates. Received: 13 November 1998     

Photoelectron spectroscopy for probing surface reactions at the CO/K/Cu(1 1 5) interface

The adsorption of carbon monoxide on the potassium modified Cu(1 1 5) surface was investigated using photoelectron spectroscopy based on synchrotron radiation. From detailed analysis of the 1s core levels in combination with existing knowledge, the assignment of surface species is performed. It is demonstrated that in dependence of the alkali coverage, several adsorption states of CO are present on the interface at 135 K. From the temperature dependence of the C 1s and O 1s profiles it is established that surface reactions based on CO dissociation start from 223 K over an interface with a potassium coverage close to half a complete K overlayer. The role of potassium as a reordering environment of adsorbed CO, leading to molecule dissociation and disproportionation is proposed. It is observed that a higher density of potassium on the substrate surface blocks adsorption sites for incoming CO molecules and no dissociation takes place.     

Deactivation of Pd particles supported on Nb2O5/Cu3Au(1 0 0): SFG and TPD studies from UHV to 100 mbar

Structural changes that occur on Pd-Nb₂O₅/Cu₃Au(1 0 0) model catalysts upon thermal annealing were followed by sum frequency generation (SFG) and temperature-programmed desorption (TPD) using CO as probe molecule. SFG experiments were performed both under ultrahigh vacuum and mbar pressure. Heating the catalyst to temperatures above 300 K lead to an irreversible 50% decrease in the CO adsorption capacity and modified the remaining adsorption sites. Alterations of the phase between resonant and non-resonant SFG signals upon annealing indicate a change in the electronic structure of the surface, which excludes Pd sintering or migration of Nb₂O₅ over Pd particles to cause the observed effect and rather suggests the formation of “mixed Pd-NbO_x” sites. The same changes in surface properties also occur during CO hydrogenation at 1 bar and high temperature, pointing to an involvement of “mixed Pd-NbO_x” sites in catalytic reactions.     

Site occupation of CO adsorbed on Ni(100) at high CO pressures

The adsorption of CO on Ni(100) has been investigated by infrared reflection-absorption spectroscopy in the temperature range of 85 to 300 K. At 300 K we achieved CO coverages up to 0.8 ML by applying CO pressures up to 1 mbar. The fraction of CO molecules adsorbed at terminal and bridge sites on Ni(100) at a fixed temperature depends strongly on the total CO coverage. The variation of the adsorption site occupancy with coverage is well reproduced by a lattice-gas model which takes into account the lateral interaction of the adsorbed molecules.     

Comparison of the interaction of Pd with positively and negatively poled LiNbO3(0 0 0 1)

To investigate the possibility of manipulating the surface chemical properties of finely dispersed metal films through ferroelectric polarization, the interaction of palladium with oppositely poled LiNbO₃(0 0 0 1) substrates was characterized. Low energy ion scattering indicated that the Pd tended to form three-dimensional clusters on both positively and negatively poled substrates even at the lowest coverages. X-ray photoelectron spectroscopy (XPS) showed an upward shift in the binding energy of the Pd 3d core levels of 0.9 eV at the lowest Pd coverages, which slowly decayed toward the bulk value with increasing Pd coverage. These shifts were independent of the poling direction of the substrate and similar to those attributed to cluster size effects on inert supports. Thus, the spectroscopic data suggested that Pd does not interact strongly with LiNbO₃ surfaces. The surface chemical properties of the Pd clusters were investigated using CO temperature programmed desorption. On both positively and negatively poled substrates, CO desorption from freshly deposited Pd showed a splitting of the broad 460 K desorption peak characteristic of bulk Pd into distinct peaks at 270 and 490 K as the Pd coverage was decreased below 1.0 ML; behavior that also resembles that seen on inert supports. It was found that a small fraction of the adsorbed CO may dissociate (<2%) for Pd on both positively and negatively poled substrates. The thermal response of the smaller Pd clusters on the LiNbO₃ surfaces, however, was different from that of inert substrates. In a manner similar to Nb₂O₅, when CO desorption experiments were carried out a second time, the adsorption capacity decreased and the higher temperature desorption peak shifted from 490 K to below 450 K. This behavior was independent of the substrate poling direction. Thus, while there was evidence that LiNbO₃ does not behave as a completely inert support, no significant differences between positively and negatively poled surfaces were observed. This lack of sensitivity of the surface properties of the Pd to the poling direction of the substrate is attributed to the three-dimensional Pd clusters being too thick for their surfaces to be influenced by the polarization of the underlying substrate.     

Electron-stimulated desorption of rare-earth metal atoms

The yield of europium and samarium atoms in electron-stimulated desorption from layers of rare-earth metals (REMs) adsorbed on the surface of oxidized tungsten has been measured as a function of the incident electron energy, surface coverage by REMs, degree of tungsten oxidation, and substrate temperature. The measurements were performed using the time-of-flight method with a surface-ionization-based detector within the substrate temperature interval 140–600 K. The yield studied as a function of electron energy has a resonance character. Overlapping resonance peaks of Sm atoms are observed at electron energies of 34 and 46 eV, and those of Eu atoms, at 36 and 41 eV. These energies correlate well with the REM 5p and 5s core-level excitation energies. The REM yield is a complex function of the REM coverage and substrate temperature. The peaks due to REM atoms are seen at low REM coverages only, and their intensity usually passes through a maximum with increasing coverage and substrate temperature. The concentration dependence of the REM atom yield is affected by the deposition of slow Ba⁺ ions, but only if they are deposited after the REM adsorption. At higher REM coverages, additional peaks are observed at electron energies of 42, 54, and 84 eV, which originate from excitation of the 5p and 5s tungsten levels and result from desorption of SmO and EuO molecules. The temperature dependence of the intensity of these peaks is explained to be due to the order-disorder phase transition. The desorption of REM atoms is the result of their reversed motion through the adsorbed REM layer, and the SmO and EuO molecules desorb due to the formation of an antibonding state between the REM oxide molecules and the tungsten ions.     

Co adsorption on potassium promoted Fe(110)

CO adsorption on potassium covered Fe(110) has been studied using UPS, XPS, AES and flash desorption. It was found that CO adsorbs molecularly at room temperature with a larger binding energy than on clean Fe(110). The CO saturation coverage increases and the sticking coefficient decreases with increasing potassium coverage. On heating, the probability of adsorbed CO dissociating increases with the amount of potassium present. The UPS spectra show that the CO 4σ peak is shifted by 0.8 eV to higher binding energies on Fe(110) + K and that at 21.2 eV the peak due to the 1π + 5σ orbitals is split into a double peak. The catalytic relevance of the measurements is discussed with reference to the Fischer-Tropsch synthesis.     

动力学晶格蒙特卡洛方法模拟Cu薄膜生长

利用动力学晶格蒙特卡洛方法模拟了Cu薄膜在Cu(100)面上的三维生长过程。模型中考虑了四个动力学过程:原子沉积、增原子迁移、双原子迁移和台阶边缘原子迁移,各动力学过程发生的概率由多体势函数确定。讨论了基底温度、沉积速率及原子覆盖率对Cu原子迁移、成核和表面岛生长等微观生长机制的影响;获得了Cu薄膜的表面形貌图并计算了表面粗糙度。模拟结果表明,随基底温度升高或沉积速率下降,岛的平均尺寸增大,数目减少,形状更加规则。低温时,Cu薄膜表现为分形的离散生长,高温时,Cu原子迁移能力增强形成密集的岛。Cu薄膜表面粗糙度随着基底温度的升高而迅速减小;当基底温度低于某一临界温度时,表面粗糙度随原子覆盖率或沉积速率的增大而增大;当基底温度超过临界温度时,表面粗糙度随原子覆盖率或沉积速率的变化很小,基本趋于稳定。     

Sticking coefficients of CO,O2 and Xe on the (110) and (100) planes of tungsten

Sticking coefficients for oxygen, CO and Xe on the (110) and (100) planes of tungsten are presented as functions of absolute coverage, surface and gas temperature. Sticking coefficients for CO are in general higher and show simpler behavior than those for oxygen. Sticking coefficients for all gases studied are higher on (100) than on (110) under comparable conditions. It is concluded that simple Kisliuk models are applicable over much of the temperature range for CO on (110) and (100), but not for oxygen, where adsorption and reflection coefficients on first impact vary with coverage, and surface and gas temperatures in complicated fashion. For Xe, at low surface temperatures sticking coefficients are close to unity and increase with coverage, indicating better energy accomodation on Xe-covered than on clean tungsten.     

Absolute coverage measurements: CO and oxygen on the (110) plane of tungsten

An effusion source, calibrated with a vibrating quartz microbalance, has been used to determine absolute coverages of CO and of oxygen adsorbed on a tungsten (110) plane by an extension of the field emitter detector method: The amount of gas reflected from the substrate is measured as a function of the absolute amount impinged per unit area; maximum coverage in the chemisorbed layer can be obtained very directly from this information. Work function increments vs. absolute coverages were measured in the same apparatus by the vibrating condenser method. Results were as follows: For virgin CO, adsorbed at 100 K, the maximum coverage obtained was CO/W = 0.71 ; this leads to a maximum coverage for beta or beta-precursor CO of CO/W = 0.28. The maximum work function increment for virgin CO was 0.8 eV. For oxygen, adsorption at 100 or 300 K a decrease in sticking coefficient by several orders of magnitude occurs when the coverage is O/W = 0.5. Adsorption at 20 K leads to the molecular precursor noted by Leung and Gomer, which converts to atomic oxygen at <50 K. By adsorbing at 20 K the O atom coverage can be increased to O/W = 0.62. Work function versus coverage data for this system are also presented.     

Influence of the metal electronic properties on the sum-frequency generation spectra of dodecanethiol self-assembled monolayers on Pt (111), Ag (111) and Au (111) single crystals

Infrared-visible sum-frequency generation (SFG) spectroscopy is performed at different visible wavelengths between 450 and 650 nm in order to investigate the interaction between metallic substrates (Pt, Ag and Au) and 1-dodecanethiol self-assembled monolayers. We show that such measurements provide a means to study the electronic properties of metals as well as the interference phenomena between the SFG signals from the adsorbate and the substrate. The common features of the three interfaces are the vibration modes of the terminal methyl groups. However, these resonances appear as peaks for Pt (111) and as dips in the case of Ag (111). Their shape is not modified when the visible wavelength is tuned between 450 and 650 nm. Moreover, the metal sum-frequency generation contribution is slightly modified in that spectral range. For Au (111) samples, the sum-frequency generation spectrum drastically evolves with the visible wavelength: the peak resonant sum-frequency generation signal at 450 nm becomes rather dip-shaped at 650 nm. The non-linear response of gold is also enhanced when the wavelength associated with the sum-frequency process is close to 480 nm. These results are interpreted on the basis of the metal electronic properties that are responsible for the non-resonant contribution to the SFG signal. Received: 15 October 2001 / Revised version: 27 March 2002 / Published online: 6 June 2002     

The coadsorption of potassium and co on the pt(111) crystal surface: A TDS,HREELS and UPS study

The interaction of CO with a potassium covered Pt(111) surface is investigated using thermal desorption (TDS), high resolution electron energy loss (HREELS) and ultraviolet photoelectron (UPS) spectroscopies. When submonolayer amounts of potassium are preadsorbed, the adsorption energy of CO increases from 25 to 36 kcal/mole, while substantial shifts in the site occupancy from the linear to the bridged site are observed. The CO stretching vibrational frequencies are shown to decrease continuously with either increasing potassium coverage or decreasing CO coverage. A minimum CO stretching frequency of 1400 cm^?1 is observed, indicative of a CO bond order of 1.5. The work function decreases by up to 4.5 eV at submonolayer potassium coverages, but then increases by 1.5 eV upon CO co-adsorption. The results indicate that the large adsorption energy, vibrational frequency and work function changes are due to molecular CO adsorption with a substantial charge donation from potassium through the platinum substrate and into the 2π¹_CO orbital.     

Adsorption of carbon monoxide on tungsten (210)

Thermal desorption spectra taken after adsorption of carbon monoxide at room temperature on W(210) show sequential formation with increasing coverage of strongly bound β₂ and β₁ binding states, correlated to the sequential formation of P(2 × 1) and (1 × 1) adsorbate structures as observed by LEED. Adsorption at room temperature gives a poorly ordered arrangement of adsorbed CO molecules, but well-ordered structures are produced by subsequent anneal. For adsorption without anneal the work function increases monotonically with coverage to a maximum of Δφ = + 0.70 eV at saturation coverage of 1 monolayer. For adsorption followed by anneal the work function dependence upon coverage is less simple, with even a decrease of work function at coverages less than a quarter monolayer. LEED intensity-voltage measurements from P(2 × 1)CO and P(2 × 1)N structures suggest that CO molecules occupy the sites of 4-fold symmetry upon which nitrogen is believed to be adsorbed. The distinction between the β₂ and β₁ states of adsorbed CO is attributed to heterogeneity induced by the reduction in binding energy of a CO molecule when its nearest-neighbor sites are occupied.