On the structure of CO adlayers on Cu(100) and Cu(111)

Alternative models for the high coverage compressed overlayers of CO on copper (100) and (111) are proposed in which the LEED patterns previously attributed to out-of-registry, uniformly compressed structures are re-interpreted in terms of adsorption on linear and bridged sites. The models provide a simpler explanation for the small influence of compression on the frequency of the infrared adsorption bond near 2000 cm^?1 compared with the large change of surface potential.     

Long-lived excited states at surfaces: Cs/Cu(111) and Cs/Cu(100) systems

One-electron and multielectron contributions to the decay of transient states in the Cs/Cu(111) and (100) systems are studied by a joined wave-packet propagation and many-body metal response approach. The long lifetime of these states is due to the Cu L and X band gaps which reduce the electron tunneling between Cs and Cu. In the (111) case, the decay is mainly by inelastic e-e interaction, whereas in the (100) case, electron tunneling is dominating. This accounts very well for the experimental findings [Bauer et al., Phys. Rev. B 55, 10 040 (1997) and Ogawa et al., Phys. Rev. Lett. 82, 1931 (1999)].     

Vibrational EELS studies of CO chemisorption on clean and carbided (111), (100) and (110) nickel surfaces

Room temperature adsorption of CO on bare and carbided (111), (100) and (110) nickel surfaces has been studied by vibrational electron energy loss spectroscopy (EELS) and thermal desorption. On the clean (100) and (110) surfaces two configurations of CO adsorbed species, namely “terminal” and bridge bonded CO, are observed simultaneously. On Ni(111), only two-fold sites are involved. The presence of superficial carbon lowers markedly the bond strength of CO on Ni(111)C and Ni(110)C surfaces, while no adsorption has been detected on the Ni(100)C surface. Moreover, on the carbided Ni(110)C surface, the adsorption mode for adsorbed CO is changed with respect to the clean surface; only “terminal” CO is then observed.     

Stabilisation of alkali-adsorbate-induced states on Cu(111) surfaces

The Li and Cs alkali-adsorbate-induced states on a model Cu(111) surface are studied theoretically using the coupled angular mode and the wave packet propagation methods. Their energy position and their decay rate via one-electron transfer into the metal are calculated. An unoccupied alkali-induced state is found with a rather long lifetime, much longer than those found in the case of free-electron metal surfaces. This is attributed to the combined effect of the hybridisation of the alkali levels and of the Cu(111) projected band gap along the normal to the surface that blocks the electron transfer between the adsorbate and the metal. This qualitatively explains the experimental finding of a long-lived state by Bauer et al. [Phys. Rev. B 55 (1997) 10 040] and Ogawa et al. [Phys. Rev. Lett. 82 (1999) 1931].     

Vibrational spectroscopy of oxygen on the (100) and (111) surfaces of lanthanum hexaboride

Reflection absorption infrared spectroscopy (RAIRS) and high resolution electron energy loss spectroscopy (HREELS) have been used to study the adsorption of oxygen on the (100) and (111) surfaces of lanthanum hexaboride. Exposure of the surface at temperatures of 95 K and above to O₂ produces atomic oxygen on the surface and yields vibrational peaks in good agreement with those observed in previous HREELS studies. On the La-terminated (100) surface, RAIRS peaks correspond to vibrations of the boron lattice that gain intensity due to a decrease in screening of surface dipoles that accompanies oxygen adsorption. A sharp peak at ～ 734 cm^?1 in the HREEL spectrum shows isotopic splitting with RAIRS into two components at 717 and 740 cm^?1 with full widths at half maxima of only 12 cm^?1. The sharpness of this mode is consistent with its interpretation as a surface phonon that is well separated from both the bulk phonons and other surface phonons of LaB₆. On the boron-terminated LaB₆(111) surface, broad and weak features are assigned to both vibrations of the boron lattice and of boron oxide. On the (100) surface, oxygen blocks the adsorption sites for CO, and adsorbed CO prevents the dissociative adsorption of O₂.     

Vibrational states of a cobalt dimer on the (111) and (001) copper surfaces

The results of calculations of the total (lateral and vertical) relaxation of the (001) and (111) copper surfaces in the presence of a small cluster of cobalt adatoms, local vibrational density of states and polarizations of these states are presented. The calculations were performed using the atomic interaction potentials in a tight binding approximation. An analysis of the results obtained showed that the presence of a cobalt dimer gives rise to modification of the vibrational states of the copper surface and generation of new modes localized both on the adatoms of the cluster and the surface atoms of the substrate. The revealed anisotropy of surface relaxation along [001] results in deformation of atomic bonding and splitting of the vibrational modes of the dimer. The lifetimes of the vibrational states of the dimer are found to be nearly equal for both surfaces under study, with a frequency shift being however observed. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 12, pp.73–78, December, 2008.     

Dynamics of image-potential states on stepped Cu(001) surfaces

The dynamical properties of image-potential states on stepped Cu(117) and Cu(118) surfaces were studied by time- and angle-resolved two-photon photoelectron spectroscopy. The interaction with the step-induced potential leads to quasielastic anisotropic scattering between image-potential-state bands. In particular, resonant interband scattering from image-potential states with quantum numbers n2 to the n=1 band and quasielastic intraband scattering within the n=1 band show high efficiency. In spite of the higher step density of Cu(117), resonant scattering is about four times larger on Cu(118). This distinction is attributed to the different step distributions of the two surfaces and to the concomitant correlation of the step arrangement on short- and long-range scales, which has been studied by scanning tunneling microscopy. Details of the surface band structure lead to different boundary conditions and may weakly affect scattering probabilities. PACS 73.20.At; 79.60.Bm; 79.60.Dp; 79.60.Ht     

Photoelectron spectroscopy of Ar/Cu(100) interface states

Buried interface states in Ar/Cu(100) were studied by means of one- and two-photon photoemission experiments. With increasing Ar overlayer thickness, a transition from broad electron scattering resonances in the Ar conduction band into a hydrogen-like series of quasi-bound states at the Ar/Cu interface was observed. The thickness dependence of energies and lifetimes is compared to theoretical resonance positions and linewidths derived from a parameterized one-dimensional potential. PACS 73.20.-r; 73.40.Ns; 79.60.-i; 78.47.+p     

Vibrational characterization of carbon monoxide adsorption on sulfur modified Ni(100) surfaces

Carbon monoxide adsorption has been studied on a series of presulfided Ni(100) surfaces using vibrational spectroscopy. The sulfided Ni(100) surfaces were characterized using Auger electron spectroscopy and low energy electron diffraction, binding states were isolated by heating CO-dosed surfaces to prescribed temperatures, corresponding to the desorption temperatures of the CO. Adsorption of CO on Ni(100) with a p(2 × 2) array of sulfur lead to CO stretching frequencies of 1740 and 1930 cm^?1 corresponding to desorption temperatures of 370 and 290 K, respectively. Adsorption of CO into the c(2 × 2)S structure resulted in a CO stretching frequency of 2115 cm^?1 and a desorption peak near 140 K. The binding sites on the p(2 × 2)S structure were interpreted as metal four-fold hollows and bridging sites. The high frequency state was interpreted as weak bonding into the four-fold hollow with back donation into the π¹ orbital on CO restricted by stearic hindrance due to adsorbed sulfur. Both the thermal desorption and vibrational results indicated that local CO-sulfur interactions are dominant on the presulfided Ni(100) surface in the coverage range studied.     

Vibrational study of the initial stages of the oxidation of Si(111) and Si(100) surfaces

Using high-resolution electron energy loss spectroscopy (EELS) the vibrations of Si(111) and Si(100) surfaces in the early stages of oxidation have been investigated. Three different stages of oxidation, the last being the formation of a thin layer of vitreous SiO₂ are identified when the surfaces are held at a temperature of 700K during the exposure with molecular oxygen. We show that also the first two stages involve atomic oxygen in bridging positions between silicon atoms. Small exposures at low temperatures (100 K) produce vibrational features of a different, possibly molecular, species. For higher exposures at the same temperature the spectrum again develops the characteristics of atomic oxygen and the molecular species eventually disappears. Exposure at room temperature leads to a mixture of atomic and molecular oxygen for smaller exposures and to purely atomic oxygen for exposures greater than 10² L. At room temperature even exposures as high as 10¹¹ L do not produce the spectrum of vitreous SiO₂. The same is found for the natural, room temperature grown, oxide layer on silicon wafers which we have studied by introducing the sample into the spectrometer through an air-lock. Annealing of the wafer to 700 K produced the characteristic spectrum of vitreous SiO₂. The results are discussed in comparison with previous work.     

Structure and electrocompression of chloride adlayers on Cu(111)

The specific adsorption of chloride on Cu(111) from acidic aqueous electrolyte (pH 3) was investigated by in-situ surface X-ray diffraction, revealing an incommensurate hexagonal rotated adlayer. The structure and its potential dependence suggest a strong adsorbate–adsorbate interaction as compared to other halide adlayers on (111)-oriented metal electrode surfaces. The orientational epitaxy can be rationalized by the model suggested by Grey and Bohr (Europhys. Lett. 18, 171, 1992), which is based on symmetry considerations.     

Theoretical investigation of image states of hydrogen covered Cu(100)

A model for atomic hydrogen covered Cu(100) is presented and the calculated energy spectrum of localized electronic states in the X gap of Cu(100) is discussed. These states form a series of unoccupied adsorption states (for n = 2,3,…) lying below the vacuum level V₀ and having energies E_n which satisfy the formula E_n = V₀−10/n²eV. The lowest state (n = 1) is expected to lie about 5.5 eV below the Fermi level.     

Unoccupied electronic states of epitaxial iron layers on Cu(100)

Inverse photoemission spectra were taken for thin epitaxial iron films on Cu(100). For a film thickness of eight monolayers the observed electronic states are characteristic for a fcc(100) surface. Thed-bands of iron show a ferromagnetic exchange splitting of 1.1 eV, considerably smaller than the bulk value of 1.8 eV, which we observe for film thicknesses above 18 monolayers.     

Time-resolved two-color interferometric photoemission of image-potential states on Cu(100)

We describe an interferometric time-resolved photoemission technique that makes it possible to simultaneously observe the decay of optical induced polarizations and populations at surfaces in a two-color excitation scheme. In this scheme initially unoccupied electronic surface states are coherently excited by the interaction of laser pulses with frequency ω_a and the two-photon polarization which is induced by laser pulses with frequency ω_a/2. Interference is observed by changing the delay between both laser pulses using an actively stabilized two-color Mach–Zehnder interferometer. We demonstrate this technique for excitation of the n=1 image-potential state on a Cu(100) surface. PACS 78.47.+p; 79.60.Bm; 73.20.-r; 82.53.Kp; 42.50.Md     

XPS and XAES study for oxidation of V/Cu(100) and V,Na/Cu(100) surfaces

Oxidation states of vanadium overlayers ( 0.1 to 2.0 ML) on a Cu(100) surface with and without sodium on the surface were investigated by XPS and XAES. The vanadium overlayers gave a V₂O₃-like surface oxide after exposure up to 600 L O₂, showing a chemical shift of the V2p_3/2 peak by 3.5 eV without coverage dependence. The surface vanadium oxide was easily oxidized further to V⁵⁺ to give a chemical shift of 5.5 eV after addition of sodium atoms on the oxide and heating at 530 K for 5 min. The high oxidation state was interpreted by a mixing of vanadium oxide and oxidized sodium. This mixing is affirmed by spectral changes showing a separation of sodium ions from the oxide during the formation of sodium acetate by adsorption of acetic acid.     

Metastable (2S) helium atom scattering from NiO(100) and Cu(100) surfaces

The scattering of metastable 2³S He atoms (He*) from cleaved NiO(100) as well as from clean and CO-covered Cu(100) surfaces has been studied. For these varied surfaces, which were characterized in situ by ground state He atom scattering, only broad He* angular distributions without any diffraction peaks were observed. For metastable He atoms scattered from the clean Cu(100) surface a total survival probability of 1×10⁻⁶ was determined. For NiO(100) and the CO-covered Cu(100) surface values of about 1×10⁻⁵ were obtained. Time-of-flight spectra of the surviving He* atoms revealed a substantial energetic broadening which increases with the substrate temperature. This behaviour indicates a large well depth for the He*–surface interaction potential and is discussed in terms of an enhanced multiphonon excitation and/or trapping probability upon the scattering.     

Image-potential states on stepped Cu (001) surfaces

Image-potential states on Cu (117) and Cu (119) surfaces were studied by means of two-photon photoelectron spectroscopy. The regular array of steps generates a lateral potential on the vicinal surfaces, which modifies the surface-electronic structure. Compared to Cu (001), the band bottom of the n=1 image-potential states shifts by 40 meV to lower binding energy. The periodicity of the step-induced superlattice manifests itself as back-folding of the n=1 and 2 dispersion bands. At the surface Brillouin zone boundary a mini-gap opens with a width of 135 meV for the first image-potential state on Cu (117). On the vicinal surfaces the lifetime of the image-potential states is reduced by a factor of three as compared to Cu (001). This is attributed to a narrowing of the surface-projected bulk-band gap when projected along the [11n] direction. While the dephasing rate of the first image-potential state is close to the decay rate, higher members of the Rydberg-like series show negligible dephasing. Received: 16 October 2001 / Revised version: 9 April 2002 / Published online: 6 June 2002