Surface phonon dispersion of Cu(100)c(2×2)N

The Cu(100) surface covered with atomic nitrogen has been studied with low energy electron diffraction (LEED), Auger electron spectroscopy (AES) and inelastic electron scattering (EELS). Atomic nitrogen, formed by thermal dissociation of NH₃ adsorbed at 100 K, forms a c(2×2) overlayer on the Cu(100) surface. The dispersion of adsorbate and substrate associated modes of the Cu(100) surface covered with a c(2×2) nitrogen overlayer has been measured along the two dimensional Brillouin zone in the - by inelastic electron scattering. The experimental data are compared to a lattice dynamical slab calculation. The Rayleigh-mode (S₄-phonon) is only slightly changed by the N-overlayer. An optimum fit for the perpendicular and parallel nitrogen modes (=320 cm^–1 and =740 cm^–1 at =0.1) is obtained when the nitrogen atom is placed 0.6 Å above the first copper layer.     

Application of the matching procedure to the calculation of phonon dispersion on Ni(100) covered with a C(2×2) overlayer

The equations of motion are worked out for the atoms of a semi-infinite crystal covered with a commensurate adsorbate by using the clean crystal as a basis. This procedure produces a complete set of displacement fields consistent with the relevant space-group symmetry. These equations are solved with help of the matching procedure to give the surface even phonon and resonance dispersion curves in the (010) direction of Ni(1OO) covered with a C(2×2) oxygen overlayer. The consequences of the adsorbate induced folding of the Brillouin zone upon the bulk and surface phonons are analysed. Using symmetry adapted coordinates secures a straightforward identification of the loss features observed by EELS.     

Carbon monoxide chemisorption on Cu(100)-c(2 × 2)Pd

Chemisorption of carbon monoxide on Cu(100)-c(2 × 2)Pd was investigated using ultraviolet photoelectron spectroscopy. Adsorption was found to occur molecularly with a saturation coverage at 100 K which is approximately the same as that on Cu(100). Desorption spectra indicate that the CO-surface bond strength for the majority of the molecules is intermediate to that for the pure metals. The 4σ satellite, characteristic of photoemission from CO on Cu, was not observed.     

Cu(111),Cu(110)和Cu(100)表面的振动弛豫

用能带理论研究了Cu(111)、Cu(110)和Cu(100)表面的振动弛豫。结果表明,第一内层间距为2.073±0.008(收缩0.53％±0.008)[对Cu(111)],1.25±0.01(收缩2.2％±0.01[对Cu(110)],1.815±0.001(膨胀0.55％±0.001)[对Cu(100)];而第二内层间距为2.15±0.01(膨胀2.2％±0.01[对Cu(111)],1.32±0.01(膨胀3.6％±0.01)[对Cu(110)],2.084±0.001(膨胀15.5％±0.001)[对Cu(100)];而第三内层间距为2.24±0.01(膨胀7.3％±0.01时Cu(111)]。     

The effect of the sulfur induced reconstruction of the Pt(S)−[6(111) × (100)] surface on CO adsorption

The effect of the sulfur induced reconstruction of the Pt(S)−[6(111) × (100)] surface on CO adsorption was investigated using thermal desorption spectroscopy (TDS). On the unreconstructed surface, desorption states are observed from the (111) terraces and from the high coordinate step edge site. Following the sulfur induced reconstruction of the surface, a new desorption state, ascribed to the upper (100) plane of the two atom high step is observed. Lateral repulsive interactions between S and CO are found to affect the desorption energy on the (111) terrace and the upper face of the (100) step edge. SuIfurCO or COCO interactions do not affect the CO desorption energy from the high coordinate step edge site. Suppression of each CO desorption state appears to be due to sulfur site blocking, as sulfur coverage is increased.     

Leed study of Fe epitaxially grown at 190°C on Cu(100)

We report a LEED study of iron deposited on Cu(100) at 190°C. Very sharp LEED patterns were obtained for high iron coverages. We observed evidence of an ill defined Fe/Cu interface for one monolayer of iron deposited at 190°C. The stability of the iron overlayers was tested as a function of time for various coverages. For one monolayer the intensity versus energy curve for the (00) beam shows time dependence at 190°C. For four layers, no significant changes were observed in the LEED spectra over a period of one hour. We measured for five layers of iron a top layer expansion of 2.8% relative to the bulk. The interplanar spacing for bulk fcc Fe at 190°C remains equal to the room value. In these experiments the samples were deposited at 190°C and kept at this temperature during the LEED measurements.     

Au and Cu Atoms on NaCl(001): a single-atom based memory device prototype?

We present a first-principle study of gold and copper atoms adsorbed in NaCl(001) surfaces. Motivated by a recent STM experiment on this subject, the electronic and magnetic properties of Au and Cu atoms are investigated, as well as the modifications in these properties under charge injection. Similarities of these systems and the corresponding isolated atom are exploited. A discussion about the possibility of applying the studied systems on high-density memory devices is addressed.     

A leed crystallographic analysis for the Cu(100)-(2 × 2)-S surface structure

An intensity analysis with low-energy electron diffraction is reported for the (2 × 2) surface structure obtained by the adsorption and presumed dissociation of H₂S on the (100) surface of copper. Intensity-versus-energy curves were measured with a video LEED analyser for five diffracted beams at normal incidence and for eleven beams at an off-normal direction with a polar angle of incidence equal to 14°. Comparisons were made with intensity curves calculated with the renormalised forward scattering method for three types of structural models in which the metal atoms remain in their regular bulk positions. The best correspondence between experimental and calculated intensities occurs with sulphur atoms adsorbed in the “expected” 4-coordinate adsorption sites. The reliability index proposed by Pendry is minimised with S atoms 1.32 Å above the topmost metal layer; this corresponds to nearest-neighbour S-Cu bond distances equal to 2.24 Å. This value appears broadly consistent with a measurement by photoelectron diffraction, as well as from model predictions.     

The effect of sulfur on co adsorption/desorption on Pt(S)-[9(111) × (100)]

CO adsorption/desorption on clean and sulfur covered Pt(S)-[9(111) × (100)] surfaces was studied using AES, TPD, and modulated beam experiments. CO desorption occurred from two states on the clean surface — a low temperature state associated with the (111) terraces and a high temperature state associated with the steps/defects. Thermal desorption results indicated that above small CO coverages conversion from the low temperature state into the high temperature state was activated and that back conversion was slow. Sulfur preferentially adsorbed at step/defect sites and decreased the population of the high temperature desorption state. Modulated beam experiments were performed in order to determine CO adsorption/desorption parameters as a function of sulfur coverage on the Pt crystal. The sticking coefficient and binding energy of CO decreased as the sulfur concentration increased. Sulfur adsorption at step/defect sites decreased the CO sticking coefficient only slightly but increased the effective rate constant for CO desorption significantly. Sulfur adsorption on the terraces affected CO adosrption more than sulfur at step sites. On the clean surface the effective rate constant for CO desorption was

$\text{1 × 10}{}^{15}\text{s}{}^{\mathrm{?1}}\text{exp (}\text{?36.2 kcal/mole}\text{RT}\text{)}$

Desorption occurred from both terrace and step/defect sites, but the kinetics were characteristic of the step/defect sites. For the surface on which step/defect sites were blocked by sulfur the effective desorption rate constant was

$\text{k}{}_{\mathrm{eff}}\text{= 1 × 10}{}^{13}\text{s}{}^{\mathrm{?1}}\text{exp (?}\text{27.5 kcal/mole}\text{RT}\text{)}$

indicating an appreciable decrease in CO binding on the terraces, though sulfur-CO repulsive interactions had probably made k_eff larger than the true rate constant for desorption from clean (111) planes. The results showed clearly a compensation effect in activation energy and preexponential factor.     

What orchestrates the self-assembly of glycine molecules on Cu(100)?

The structures of two competing phases and their interrelationship in the self-organization of glycine molecules on a Cu(100) surface were clarified. Despite their similar structural energies predicted using first-principles calculation, completely different mechanisms were found to stabilize the two phases. The balance and coordination of the two mechanisms that induce a variety of self-assembled structures in this attractive system were revealed. Furthermore, the importance of the microscopic arrangement of the molecules in designing the macroscopic electronic structures was directly demonstrated.     

Methane dehydrogenation on monomeric Rh center located on (100) γ-alumina — A theoretical study

The reaction mechanism of methane dehydrogenation on monomeric Rh center located on (100) γ-alumina has been theoretically investigated at the PBE0/cc-pVTZ, SDD level. The (100) face of γ-alumina support is represented by an Al₈O₂₆H₂₈ cluster, which is cut out from the ideal crystal structure. Then, two model Rh/γ-Al₂O₃ catalysts, in which Rh center interacts with one oxygen or two oxygen atoms of the (100) surface of γ-Al₂O₃, have been compared and denoted as Rh/Al₈O₂₆H₂₇ and Rh/Al₈O₂₆H₂₆, respectively. Toward methane activation, the model catalyst Rh/Al₈O₂₆H₂₇ exhibits better performance than Rh/Al₈O₂₆H₂₆. For the first CH bond cleavage of methane, the lowering of activation barriers on Rh/Al₈O₂₆H₂₇ is mainly caused by lower substrate activation strain ΔE^≠_strain[substr], which is from substrate equilibrium geometry to the geometry it adopts in the TS, in comparison with that on Rh/Al₈O₂₆H₂₆. These results are in qualitative agreement with the experimental results, where the partially reduced Rh⁺ is one of the active sites for methane dissociation.     

DFT study of isocyanate chemisorption on Cu(100): Correlation between substrate–adsorbate charge transfer and intermolecular interactions

The adsorption of isocyanate (? NCO) species on Cu(100) was studied using the density functional theory (DFT) and the periodic slab model. The calculations indicate that at low and intermediate coverages NCO adsorbs preferentially on bridge and hollow sites. Work function and dipole moment changes show a significant negative charge transfer from Cu to NCO. The resulting charged NCO species interact repulsively among themselves being these dipole–dipole interactions particularly intensive when they are adsorbed in adjacent sites. Consequently, isocyanates tend to be separated from each other generating the vacant sites required for the dissociation to N and CO. This condition for NCO dissociation has been suggested in the past from experimental observations. A comparison was also performed with the NCO adsorption on Pd(100). In particular, the calculated minimal energy barrier for NCO dissociation was found to be higher on Cu(100) than on Pd(100) in accord with the well known higher NCO stability on Cu(100).     

Molecular and atomic adsorption states of oxygen on Cu(111) at 100–300 K

Adsorption states of oxygen on Cu(111) at 100–300 K were investigated by means of HREELS. Two molecular species were characterized by different OO stretching frequencies (v(OO)) at 610 cm⁻¹ and 820–870 cm⁻¹, which are assigned to the peroxo-like species (O²⁻₂) adsorbed in a bridged form and the one in a bidentate form bound on an atop site, respectively. The bridged peroxo species is preferred at the low coverage and the atop peroxo species becomes dominant at the higher coverage. In addition to the peaks due to the molecular oxygen, a peak assigned to v(CuO) of atomic oxygen was observed at 370 cm⁻¹ at the high coverage. The frequency of this mode was higher than the frequency reported for Cu(111) exposed to oxygen above 300 K, indicating that the adsorption state of atomic oxygen formed at 100 K is different from that above 300 K. The v(OO) modes became faint after annealing to 170 K because of O₂ dissociation. The v(CuO) mode of the atomic oxygen formed at 100 K remained up to 230 K and disappeared after annealing to 300 K. No desorption of O₂ was detected on annealing to 300 K. It was also found that vibrational spectra for adsorbed NH₃ are influenced by the adsorption states of atomic oxygen on Cu(111).