Cluster and periodic DFT calculations of adsorption and activation of CO2 on the Cu(hkl) surfaces

The adsorption behavior and thermal activation of carbon dioxide on the Cu(1 1 1), Cu(1 0 0), and Cu(1 1 0) surfaces have been investigated by means of density functional theory calculations and cluster models and periodic slabs. According to the cluster models, the optimized results indicate that the basis set of C and O atoms has a distinct effect on the adsorption energy, but an indistinct one on the equilibrium geometry. For the CO₂/Cu(hkl) adsorption systems studied here, the final structure of adsorbed CO₂ is near linear and the preferred modes for the adsorption of CO₂ onto the Cu(1 1 1), Cu(1 0 0), and Cu(1 1 0) surfaces are the side-on adsorption at the cross bridge site with an adsorption energy of 13.06 kJ/mol, the side-on adsorption at the short bridge site (13.54 kJ/mol), and the end-on adsorption on the on-top site with C–O bonds located along the short bridge site (26.01 kJ/mol), respectively. However, the calculated adsorption energies from periodic slabs are lower as compared to the experimental data as well as the cluster model data, indicating that the periodic slab approach of generalized gradient approximation in the density function theory may be not suitable to obtain quantitative information on the interaction of CO₂ with Cu(hkl) surfaces.     

Quantum-well states in bilayers of Ag and Au on W(1 1 0)

sp-Like quantum-well states (QWS) in thin monocrystalline bilayer films of Ag and Au on W(1 1 0) and of single Ag films were studied by angle-resolved photoemission. We find that the propagation of the electronic states in the bilayer films along [1 1 1] depends on the energy relative to the band edge of Au metal at the L point of the Brillouin zone. In particular, QWS with binding energies less than this band-edge energy (1.1 eV) are strongly confined to the Ag layer, while for higher binding energies the QWS extend across the whole bilayer film. This clearly demonstrates the weakness of the potential barrier at the Ag/Au interface in the context of QWS formation at energies where electronic states exist in both metals.     

Surface properties of Hafnium diboride(0 0 0 1) as determined by X-ray photoelectron spectroscopy and scanning tunneling microscopy

The surface structure and properties of the HfB₂(0 0 0 1) (Hafnium diboride, HfB₂) surface have been investigated with X-ray photoelectron spectroscopy, low energy electron diffraction (LEED), and scanning tunneling microscopy (STM). Annealing temperatures above 1900°C produce a sharp (1×1) LEED pattern, which corresponds to STM images showing flat (0 0 0 1) terraces with a very low contamination level separated by steps 3.4 Å in height, corresponding to the separation of adjacent Hf planes in the HfB₂ bulk structure. For lower annealing temperatures, extra p(2×2) spots were observed with LEED, which correspond to intermediate terraces of a p(2×1) missing row structure as observed with STM.     

A PdO(1 0 1) thin film grown on Pd(1 1 1) in ultrahigh vacuum

We present experimental results demonstrating that a high quality PdO(1 0 1) thin film can be grown on Pd(1 1 1) in ultrahigh vacuum by oxidizing the metal at 500 K using an oxygen atom beam, followed by annealing to 675 K. Low energy electron diffraction (LEED) images show that the [0 1 0] direction of the PdO(1 0 1) thin film aligns with the [−1 1 0] direction of the Pd(1 1 1) substrate, and that the PdO film grows in three degenerate domains, rotated 120° relative to one another. Based on excellent agreement between the experimental and simulated LEED patterns, we conclude that the surface structure of the PdO thin film deviates minimally from bulk-terminated PdO(1 0 1). Recent temperature programmed desorption (TPD) experiments also provide evidence that the PdO(1 0 1) thin film on Pd(1 1 1) is terminated by the stoichiometric surface in which half of the Pd atoms are coordinatively unsaturated (cus), corresponding to a cus-Pd atom density equal to about 35% of the surface density of Pd(1 1 1). The ability to generate a well-defined PdO(1 0 1) surface in ultrahigh vacuum should provide new opportunities for conducting model surface science studies of PdO, particularly studies aimed at elucidating the reactivity of PdO(1 0 1) toward species important in commercial applications of Pd catalysis.     

Core-level spectroscopy of the Pd/W(1 1 0) interface: Evidence of long-range Pd-island-W interactions at submonolayer Pd coverages

We have measured W 4f_7/2 core-level photoemission spectra from W(1 1 0) in the presence of Pd overlayers for coverages up to ∼1 pseudomorphic monolayer (ML). At coverages close to 0.05 ML a striking change in the W core-level spectrum is observed, which we interpret as indicating a long-range lateral effect of 2D Pd islands upon the W electronic structure in both the first and second W layers. As the coverage increases the long-range effect weakens and finally vanishes near 0.85 ML. Above this coverage the W spectra are typical for a W-based bimetallic interface, with the first-layer W atoms exhibiting a small interfacial core-level shift (−95 ± 5 meV) compared to the bulk atoms.     

Adsorption of oxygen and carbon dioxide on cesium-reconstructed Ag(1 1 0) surface

The adsorption of oxygen and carbon dioxide on cesium-reconstructed Ag(1 1 0) surface has been studied with scanning tunneling microscopy (STM) and temperature programmed desorption (TPD). At 0.1 ML Cs coverage the whole surface exhibits a mixture of (1 × 2) and (1 × 3) reconstructed structures, indicating that Cs atoms exert a cooperative effect on the surface structures. Real-time STM observation shows that silver atoms on the Cs-covered surface are highly mobile on the nanometer scale at 300 K. The Cs-reconstructed Ag(1 1 0) surface alters the structure formed by dissociative adsorption of oxygen from p(2 × 1) or c(6 × 2) to a p(3 × 5) structure which incorporates 1/3 ML Ag atoms, resulting in the formation of nanometer-sized (10–20 nm) islands. The Cs-induced reconstruction facilitates the adsorption of CO₂, which does not adsorb on unreconstructed, clean Ag(1 1 0). CO₂ adsorption leads to the formation of locally ordered (2 × 1) structures and linear (2 × 2) structures distributed inhomogeneously on the surface. Adsorbed CO₂ desorbs from the Cs-covered surface without accompanied O₂ desorption, ruling out carbonate as an intermediate. As a possible alternative, an oxalate-type surface complex [OOC–COO] is suggested, supported by the occurrence of extensive isotope exchange between oxygen atoms among CO₂(a). Direct interaction between CO₂ and Cs may become significant at higher Cs coverage (>0.3 ML).     

Structure and electronic properties of ultrathin Co films on W(1 1 0)

The structure and electronic properties of ultrathin Co films on W(1 1 0) grown by molecular beam epitaxy in UHV were investigated by low energy electron diffraction (LEED) and scanning tunneling microscopy and spectroscopy (STM and STS). For coverages above 0.7 ML the pseudomorphic (ps) monolayer is transformed gradually into close-packed (cp-) monolayer areas, showing up as separated islands that increase in size with coverage until the cp-monolayer is complete. Two different structures of the cp-monolayer were observed by atomically resolved STM, both leading to a 8 × 1 superstructure in the LEED pattern. Higher coverages continue to grow in the Stransky–Krastanov growth mode forming simultaneously double layer islands and triple layer islands in fcc(1 1 1) and hcp(0 0 0 1) stacking. STS reveals tunneling spectra that differ considerably depending on the thickness and on the structure. Two different classes of triple layer islands can be distinguished by a resonant peak at +0.3 eV appearing in only one of the two classes. We attributed this behavior to a different stacking according to a fcc or hcp structure.     

Density functional theory analysis of the Ni(1 1 0)c(2 × 2)-CN surface phase

Density functional theory slab calculations have been used to investigate the structure of the Ni(1 1 0)c(2 × 2)-CN adsorption phase. The results show excellent agreement with experimental quantitative determinations of this structure by photoelectron diffraction and low energy electron diffraction. In particular, they show that a lying-down orientation with the C–N axis along [0 0 1] perpendicular to the close-packed Ni rows on the surface is strongly favoured over end-on adsorption (with the C–N axis perpendicular to the surface). This geometry is also favoured over a lying-down geometry with the C–N axis aligned along the azimuth, as originally proposed for this system and supported by cluster calculations.     

Structure of the neopentane monolayer adsorbed on MgO(0 0 1): experiments and calculations

The monolayer of C(CH₃)₄ molecules adsorbed upon a highly homogeneous MgO powder surface has been studied by means of neutron diffraction techniques at the temperature 210 K. The structure of the monolayer presents a strong commensurability c(2 × 4) with the MgO(0 0 1) surface. The results of potential calculations support the proposed structure.     

Structures of sulfur on TiO2(1 1 0) determined by scanning tunneling microscopy, X-ray photoelectron spectroscopy and low-energy electron diffraction

The temperature dependent adsorption of sulfur on TiO₂(1 1 0) has been studied with X-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy (STM), and low-energy electron diffraction (LEED). Sulfur adsorbs dissociatively at room temperature and binds to fivefold coordinated Ti atoms. Upon heating to 120°C, 80% of the sulfur desorbs and the S 2p peak position changes from 164.3±0.1 to 162.5±0.1 eV. This peak shift corresponds to a change of the adsorption site to the position of the bridging oxygen atoms of TiO₂(1 1 0). Further heating causes little change in S coverage and XPS binding energies, up to a temperature of 430°C where most of the S desorbs and the S 2p peak shifts back to higher binding energy. Sulfur adsorption at 150°C, 200°C, and 300°C leads to a rich variety of structures and adsorption sites as observed with LEED and STM. At low coverages, sulfur occupies the position of the bridging oxygen atoms. At 200°C these S atoms arrange in a (3×1) superstructure. For adsorption between 300°C and 400°C a (3×3) and (4×1) LEED pattern is observed for intermediate and saturation coverage, respectively. Adsorption at elevated temperature reduces the substrate as indicated by a strong Ti³⁺ shoulder in the XPS Ti 2p_3/2 peak, with up to 15.6% of the total peak area for the (4×1) structure. STM of different coverages adsorbed at 400°C indicates structural features consisting of two single S atoms placed next to each other along the [0 0 1] direction at the position of the in-plane oxygen atoms. The (3×3) and the (4×1) structure are formed by different arrangements of these S pairs.     

Photoelectron holography analysis of W(1 1 0)(1×1)–O surface

By applying photoelectron holography analysis to a W(1 1 0)(1×1)–O surface, the real space image was reconstructed around the oxygen atoms. The peak positions showed that the oxygen atoms lie within the top layer, which does not contradict the results of the R-factor X-ray photoelectron diffraction analysis of Daimon et al. [Surf. Sci. 408 (1998) 260]. The holographic analysis of the calculated photoelectron diffraction pattern indicated that holographic reconstruction reveals atomic positions up to the third nearest-neighbor scatterers. Our study suggests the possibility that the distance among the adsorbate oxygen atoms is slightly larger than the lattice constant of the substrate.     

LEED structure determination of the Ni(1 1 1)(√3×√3)R30°-Sn surface

Quantitative low energy electron diffraction has been used to determine the structure of the Ni(1 1 1)(√3×√3)R30°-Sn surface phase. The results confirm that the surface layer comprises a substitutional alloy of composition Ni₂Sn as previously found by low energy ion scattering (LEIS), and also shows that there is no stacking fault at the substrate/alloy interface as has been found in (√3×√3)R30°-Sb surface alloys on Ag and Cu(1 1 1). The surface alloy layer is rumpled with the Sn atoms 0.45 ± 0.03 Å higher above the substrate than the surrounding Ni atoms. This rumpling amplitude is almost identical to that previously reported on the basis of the LEIS study. Comparison with similar results for Sn-induced surface alloy phases on Ni(1 0 0) and Ni(1 1 0) shows a clear trend to reduced rumpling with reduced surface atomic layer density, an effect which can be rationalised in terms of the different effects of valence electron charge smoothing at the surface.     

Local Au coverage as driving force for Au induced faceting of vicinal Si(0 0 1): a LEEM and XPEEM study

Adsorption of Au at 850°C on a regular stepped 4° vicinal Si(0 0 1) surface results in a dramatic change of the step morphology: the surface decomposes into areas which are perfectly flat with a (0 0 1) orientation and (1 1 9) facets. Low energy electron microscopy shows the dynamics of the faceting process in real space while X-ray photoemission electron microscopy (XPEEM) allows a spatially resolved determination of the Au coverage at different stages of the faceting process. At a critical Au coverage of ≈1/3 ML (0 0 1) terraces are formed which extend anisotropically along the step edges of the surface. The steps in between the terraces bunch and form step bands in order to conserve the macroscopic miscut of the sample. Driving force for this morphological transformation is a complex (5×3.2) reconstruction formed on the (0 0 1) terraces. XPEEM shows this phase separation also for the Au coverage: on the (0 0 1) terraces the Au coverage is up to 40% higher compared to the step bands. With further increasing Au coverage the width of the Au rich terraces increases while the step bands become steeper. In a second step Au adsorbs on the step bands transforming them into well defined and smooth (1 1 9) facets.     

Core-level shifts at the Pt/W(1 1 0) monolayer bimetallic interface

We have measured W and Pt 4f_7/2 core-level photoemission spectra from interfaces formed by ultrathin Pt layers on W(1 1 0), completing our core-level measurements of W(1 1 0)-based bimetallic interfaces involving the group-10 metals Ni, Pd, and Pt. With increasing Pt coverage the sequence of W spectra can be described using three interfacial core-level peaks with binding-energy (BE) shifts (compared to the bulk) of −0.220 ± 0.015, −0.060 ± 0.015, and +0.110 ± 0.010 eV. We assign these features to 1D, 2D pseudomorphic (ps), and 2D closed-packed (cp) Pt phases, respectively. For ∼1 ps ML the Pt 4f_7/2 BE is 71.40 ± 0.02 eV, a shift of +0.46 ± 0.09 eV with respect to the BE of bulk Pt metal. The W 4f_7/2 core-level shifts induced by all three adsorbates are semiquantitatively described by the Born-Haber-cycle based partial-shift model of Nilsson et al. [39]. As with Ni/W(1 1 0), the difference in W 4f_7/2 binding energies between ps and cp Pt phases has a large structural contribution. The Pt 4f lineshape is consistent with a small density of states at the Fermi level, reflective of the Pt monolayer having noble-metal-like electronic structure.     

Morphological anisotropy during migration enhanced epitaxy of GaAs(0 0 1)

The GaAs(0 0 1) surface morphology and structure during growth by migration enhanced epitaxy (MEE) has been studied by reflection high energy electron diffraction and scanning tunneling microscopy. Changes induced by varying the incident As/Ga flux ratio, growth temperature and the total amount of material deposited in each cycle have been studied and the results compared with GaAs(0 0 1) growth by conventional molecular beam epitaxy (MBE). Comparison of the surface morphology at the end of the Ga and As cycles indicates no clear evidence for any enhancement in the Ga adatom diffusion length during the Ga cycle. However, the morphological anisotropy of the growth front does change significantly and it is proposed that this changing anisotropy during MEE enables Ga adatom diffusion along both azimuths. The surface anisotropy during MEE growth is found to increase with the Ga/As ratio. Although there is a clear correlation between composition and morphology, we have also found that highly ordered and flat surfaces are not necessarily an indication of stoichiometric material. We also attempt to clarify a recent controversy on the structure of the c(4 × 4) reconstruction by studying the surface structure at the end of the As cycle as a function of the As/Ga ratio.     

Surface vs. bulk magnetic properties of Co/Fe(0 0 1) and Fe/Co/Fe(0 0 1) as probed by linear magnetic dichroism in photoemission

The atomic-like behavior of the photoionization cross-section of core levels in solids is remarkably displayed in the observation of linear magnetic dichroism in the angular distribution (LMDAD) of photoelectrons. Nevertheless, structure-related effects are clearly visible as modulations of the dichroism signal, induced by photoelectron diffraction (PED). In this paper a comparison between the PED and LMDAD behaviours is presented for Fe 3p in Fe(0 0 1). In order to separate experimentally the surface and bulk contributions, ultrathin Co/Fe pseudomorphic overlayers were grown on the Fe(0 0 1) surface. Results confirms the PED nature of LMDAD modulations, which can be used as an estimate of the bulk sensitivity of the experiment.     

Desorption induced by hot electrons: wave packet calculation of CO on Cu surfaces

A quantum mechanical photodesorption model, valid for metallic substrates and sub-picosecond laser pulses, is presented. It takes into consideration the photodesorption coordinate and models the metal hot-electron mediated desorption by a three electronic states: an ionic state of the adsorbate and two effective states representing the continuum of the metal. This multiple-state picture allows the sharing of the flow of energy injected by the laser between the adsorbate and the substrate. For the first time, the present modeling introduces the hot electrons of the metal through an optical potential based on the kinetic model developed earlier by the authors. This potential, and the resulting desorption yield, depend on the laser fluence. For CO on Cu(1 0 0) or Cu(1 1 1), the results are in fair agreement with the experimental findings.     

Electron spectroscopy studies of surface In-Ag alloy formation on the tungsten surface

XPS and UPS investigations of ultrathin films of In/Ag and Ag/In, deposited onto the W(1 1 0) surface in the ultrahigh vacuum conditions have been performed. Indium and silver films were formed by “in-situ” evaporation on W(1 1 0) substrate. XPS and UPS studies have been performed by means of SCIENTA ESCA200 instrument. The changes of In4d core-level and Ag4d valence band emissions with increasing Ag and In coverage were monitored to observe the energy shift and shape of the spin-orbit doublet of In4d and Ag4d lines in the Ag/In/W and In/Ag/W systems. UPS (HeI and HeII) measurements were supported by XPS AlK_α measurements of In3d and W4p levels, as well as by investigations of Ag3d levels. XPS and UPS data allowed to evaluate the coverage and make conclusions concerning intermixing and surface alloying in the In/Ag/W and Ag/In/W systems. W(1 1 0) substrate can be cleaned after each deposition by thermal desorption and no alloying in the In/W and Ag/W systems is observed.     

The IR spectra of Mg5C(CO) complexes on the (0 0 1) surfaces of polycrystalline and single crystal MgO

The FTIR spectroscopy of carbon monoxide adsorbed on polycrystalline MgO smoke has been investigated as a function of the CO equilibrium pressure at constant temperature (60 K) (optical isotherm) and of the temperature (in the 300–60 K range) at constant CO pressure (optical isobar). In both cases the spectra fully reproduce those of CO adsorbed on the (0 0 1) surface of UHV cleaved single crystals [Heidberg et al., Surf. Sci. 331–333 (1995) 1467]. This result, never attained in previous investigations on dispersed MgO, contribute to bridging the gap which is commonly supposed to exist between surface science and the study of “real” (defective) systems. Depending on the surface coverage θ the main spectral features due to the CO/MgO smoke interaction are a single band shifting from 2157.5 (at θ→0) to 2150.2 cm⁻¹ (at θ=1/4) or a triplet, at 2151.5, 2137.2 and 2132.4 cm⁻¹ (at θ>1/4). These manifestations are due to the ν(CO) modes of Mg_5C²⁺· · · CO adducts formed on the (0 0 1) terminations of the cubic MgO smoke microcrystals. The formation of the CO monolayer is occurring in two different phases: (i) a first phase with CO oscillators perpendicularly oriented to the surface (2157–2150 cm⁻¹) and (ii) a second phase constituted by an array of coexisting perpendicular and tilted species (triplet at 2151.5, 2137.2 and 2132.4 cm⁻¹). A much weaker feature at 2167.5–2164 cm⁻¹ is assigned to Mg_4C²⁺· · · CO adducts at the edges of the microcrystals. The heat of adsorption of the perpendicular Mg_5C²⁺· · · CO complex in the first phase has been estimated from the optical isobar and results to be 11 kJ mol⁻¹.     

A single h-BN layer on Pt(1 1 1)

The structure and formation of an ultrathin hexagonal boron nitride (h-BN) film on Pt(1 1 1) has been studied by a combination of scanning tunneling microscopy, low energy electron diffraction, low energy electron microscopy, X-ray absorption and high resolution core level spectroscopy. The study shows that a single boron nitride layer is formed on Pt(1 1 1), resulting in a coincidence structure. High resolution scanning tunneling microscopy (STM) images of the h-BN ultrathin film display only one of the atomic species in the unit cell. Probing the boron and nitrogen related local density of states by near edge X-ray absorption fine structure measurements we conclude that the nitrogen sublattice is visible in STM images. The growth of the single hexagonal boron nitride layer by vapourized borazine in the pressure range of 1×10^-6–1×10^-8 at 800 °C is further studied by low energy electron microscopy, and reveals that the number of nucleation sites and the perfection of the growth is strongly pressure dependent. A model for the single, hexagonal, boron nitride layer on Pt(1 1 1) is proposed.