Chemisorption of carbon monoxide on platinum {111}: Reflection-absorption infrared spectroscopy

Reflection-adsorption infrared spectroscopy has been combined with thermal desorption and surface stoichiometry measurements to study the structure of CO chemisorbed on a {111}- oriented platinum ribbon under uhv conditions. Desorption spectra show a single peak at coverages > 10¹⁴ molecules cm^?2, with the desorption energy decreasing with increasing coverage up to 0.4 of a monolayer, and then remaining constant at ≈135 kJ mol^?1 until saturation. The “saturation” coverage at 300 K is 7 × 10¹⁴ molecules cm^?2, and no new low temperatures state is formed after adsorption at 120 K. Infrared spectra show a single very intense, sharp band over the spectral range investigated (1500 to 2100 cm^?1), which first appears at low coverages at 2065 cm^?1 and shifts continuously with increasing coverage to 2101 cm^?1 at 7 × 10¹⁴ molecules cm^?2. The halfwidth of the band at 2101 cm^?1 is 9.0 cm^?1, independent of temperature and only slightly dependent on coverage. The band intensity does not increase uniformly with increasing coverage, and hysteresis is observed between adsorption and desorption sequences in the variation of both the band intensity and frequency as a function of coverage. The frequency shift and the virtual invariance of the absorption band halfwidt with increasing coverage (Jespite recent LEED evidence for overlayer compression in this system) are attributed to strong dipole-dipole coupling in the overlayer.     

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.     

Is two-dimensional metallic hydrogen possible on a {111} platinum surface?

The structure of a partially covered Pt surface with hydrogen is investigated for some typically metallic interactions. It is necessary to have an oscillatory interaction to get the observed structure of Weinberg and Merril, with any reasonable choice of core radius. Experiment are suggested to get at the metallic hydrogen layer Pt surface distance, as well as the registry of the plane of protons relative to the surface layer of Pt.     

Precursor mediated and direct adsorption of molecular nitrogen on Fe{111}

In this article, we will summarize the kinetic models for nitrogen dissociation on Fe {111} and will present new data on the adsorption mechanism for the -bonded -N₂ state, which was identified as the immediate precursor for dissociation. Our results reveal that adsorption into the state can occur via the more weakly bonded state, but also by direct impact from the gas phase. The sticking coefficient via the state precursor depends directly on its concentration, and therefore depends on the temperature of the substrate and the gas pressure. Contrary to our previous estimates, the kinetic parameters for precursor mediated adsorption into the state in the limit of zero coveragecannot explain the high temperature dissociation probability. The direct channel from the gas phase into the state needs to be included to explain the experimental results. We also discuss the stabilization of -N₂ by preadsorbed -N₂, i.e. an attractive interaction between alike molecules but in different bonding configurations.Balzers, ELS Abteilung, FL-9496 Balzers, Fürstentum Liechtenstein     

Electron energy loss spectroscopy of A {111} oriented aluminum single crystal

Recently, the electron energy loss spectroscopy (ELS) and secondary electron spectroscopy (SES) of the interaction of oxygen with polycrystalline aluminum were reported for primary energies in the range 30 ? E_p ? 250 eV. Two new transitions were resolved in the ELS spectra (one at 4 eV for clean aluminum and the other at 12 eV for oxide-covered aluminum) for low primary energies (E_p ~ 30 eV). In this paper we report on experiments utilizing a {111} oriented single crystal of aluminum that confirm the existence of these loss peaks for low primary energies and show that the 4 eV peak position for pure aluminum depends on the primary beam energy. This suggests that this low energy loss peak is due to direct nonvertical inter- and intraband transitions which differs from the previous assignment.     

Atomic structure of Fe {111}

A clean Fe {111} surface was prepared and studied with LEED (low-energy electron diffraction) and AES (Auger electron spectroscopy). A LEED intensity analysis was carried out with a new computational scheme (THIN) specially designed for short interlayer spacings. The results are, for the fust interlayer spacing, d₁₂ = 0.70 ± 0.03 Å and for the inner potential V₀ = 11.1 ± 1.1 eV, the confidence intervals referring to 95% confidence level. Thus, the Fe {111} surface is contracted 15.4% with respect to the bulk (0.827 Å).     

Bulk-like structure of diamond {111}

A LEED (low-energy electron diffraction) intensity analysis of C {111} 1 × 1 (diamond) has given good agreement with a surface structure which has bulk positions with small relaxation of the first interlayer spacing for both insulating and semiconducting specimens. The truncated-bulk character of C{111} 1 × 1 gives support to the previously determined bulk-like structure of stabilized Si{111} 1 × 1, and casts doubt on the disordered 7 × 7 structure suggested for the stabilized 1 × 1 phase by interpretation of photoemission measurements. In both cases rather than doubt the LEED structure, one can doubt the interpretation of the photoemission measurements.     

Chemisorption and reactivity of furan on Pd{111}

XPS, HREELS, ARUPS and Δø data show that furan chemisorbs non-dissociatively on Pd{111} at 175 K, the molecular plane being significantly tilted with respect to the surface normal. Bonding involves both the oxygen lone pair and significant π interaction with the substrate. The degree of decomposition that accompanies molecular desorption is a strong function of coverage: 40% of the adsorbate desorbs molecularly from the saturated monolayer. Decomposition occurs via decarbonylation to yield CO_a and H_a followed by desorption rate limited loss of H₂ and CO. It seems probable that an adsorbed C₃H₃ species formed during this process undergoes subsequent stepwise dehydrogenation ultimately yielding H₂ and C_a.     

Adsorption and desorption of no from Rh{111} and Rh{331} surfaces

The adsorption and desorption chemistry of NO on the clean Rh{111} and Rh{331} single crystal surfaces was followed with SIMS, XPS, and LEED. Results suggest dissociative NO adsorption occurs at step and/or defect sites. At saturation coverage there was ～ 10 times more dissociated species on the Rh{331} surface at 300 K than on the Rh{111} surface. On both surfaces two molecular states of NO_ads have been identified as β₁, and β₂ which possess different chemical reactivity. Under the condition of saturation coverage the β₁ and β₂ states are populated on the Rh{111} surface in a different proportion than on the Rh{331} surface. Further, their population on both surfaces is coverage and temperature dependent. When the sample is heated to desorb the saturation overlayer formed on the Rh{111} and Rh{331} crystal surfaces, approximately 50% of the overlayer is found to desorb below ? 400 K primarily from the β₂ state, molecularly as NO(g). Between 300 and 400 K the β₁ state dissociates as binding sites necessary to coordinate N_ads and O_ads are freed by desorption of NO(g).     

Island formation during CO/H coadsorption on Pt{111} studied by IR reflection-absorption spectroscopy

The reversible formation of pure CO islands during the coadsorption of CO and H on Pt{111} has been followed by monitoring the internal stretching vibration as well as the metal-carbon stretch of the CO molecule using infrared reflection-absorption spectroscopy. Island formation occurs in the temperature range 100 < T < 180 K and for average CO coverages θ_co < 0.25. This can be inferred from the appearance of bridge-bonded CO, not normally present on Pt{111} in this coverage range, and from the frequency and lineshape behaviour of the on-top absorption band. Depending on temperature and average CO coverage islands with local coverages up to θ'_CO = 0.5 occur but they always coexist with regions of lower local coverage and/or size. There is only a very weak direct interaction between the two species on the surface.     

Time-resolved photoelectron spectroscopy of $\mathrm{Al}_{3}\mathrm{O}_{3}^{-}$: photoisomerization versus photofragmentation

In general, clusters are unstable and in many cases several metastable isomers exist even at low temperature. Therefore, a cluster may react with a dramatic geometry change to a small disturbance such as a weak field or to the absorption of a low-energy photon. Here, we study the response of Al₃O₃^-\mathrm{Al}_{3}\mathrm{O}_{3}^{-} to photoexcitation using time-resolved photoelectron spectroscopy. Earlier experimental and theoretical studies suggested that this cluster anion undergoes a geometry change after photoexcitation. In contrast, our time-resolved spectra indicate that photoexcitation triggers ultra-fast fragmentation. This example demonstrates that ultra-fast processes in clusters are not well understood and that it is still difficult to gain reliable experimental data about such processes.     

Damage studies on the system^{111} \mathop {In}\limits^ \to \underline {Ni}

Lattice damage after implantation of¹¹¹In in Ni has been studied applying the DPAC technique to the 171–245 keV -ray cascade in the daughter nucleus¹¹¹Cd. Implantations were carried out at 10 K and at 300 K. The low temperature implantation yields a higher regular substitutional fraction (80%) than the room temperature implantation (40%). The annealing behaviour of both implants above RT is the same. In addition, two distinct defect-associated sites were observed in isochronal annealing sequences. A microscopic model for these defects is presented, which takes into account magnetic and electric hyperfine interaction strengths, binding energies and site populations as a functions of temperature.     

Si｛111｝的吸附表面结构

利用低能电子衍射研究了金属和非金属吸附在Ｓｉ｛１１１｝表面的表面结构。结果显示出：对Ａｌ、Ｇａ、Ｂｉ和Ａｕ原子，形成α－Ｓｉ｛１１１｝３×３Ｒ３０°－Ｍ或β－Ｓｉ｛１１１｝３×３Ｒ３０°－Ｍ结构的共价吸附。对Ｌｉ、Ｎａ和Ａｇ原子，形成正离子吸附，全部经高温解吸后，便诱导出Ｓｉ｛１１１｝１×３重构。对Ｔｅ原子，形成负离子吸附，经高温解吸后，便诱导出Ｓｉ｛１１１｝类（１×１）结构。     

Electron states and atomic positions at the {001}, {110} and {111} faces of W and Mo

The results of ab initio calculations on the {001}, {110} and {111} surfaces of W and Mo and on the (√2 × √2)R45° reconstructed W {001} surface are presented. A distribution of surface states in reasonable agreement with experiment is found. A simple parametrisation of the short range repulsive force between transition metal atoms is used to predict, for all these surfaces, relaxations which are comparable with those observed. This same parametrisation indicates that the W and Mo {001} surfaces are stable to proposed reconstructive displacements.     

Ferromagnetic resonance relations in {111}-oriented garnet films

Microwave resonance relations for a {111} garnet film have been derived including the uniaxial as well as the first and second order cubic anisotropy contributions. Special attention has been given to the in-plane resonance condition. For this case the calculation has been made up to second order inK ₁/MH andK ₂/MH taking into account the influence of a nonideal in-plane configuration of the film.The author wishes to express his thanks to Dr. Z. Frait for valuable discussions.