Unusually low stretching frequency for CO adsorbed on Fe(100)

For CO adsorption on Fe(100) different adsorption species are detected with high resolution EELS (electron energy loss spectroscopy) which sequentially fill in with increasing coverage. Up to ～ 350 K and low CO exposure (≦1 L), a predominant molecular species with an unusually low stretching frequency, 1180–1245 cm^?1, is detected. This unusual CO bond weakening is consistent with a “lying down” binding configuration of CO. For higher CO coverages at 110 K, further CO adsorption states with vibrational frequencies of 1900–2055 cm^?1 are populated which are due to CO bound with the molecular axis perpendicular to the surface.     

Ion angular distributions in electron stimulated desorption: Oxygen and CO on W(111)

The ion angular distributions resulting from electron stimulated desorption (ESD) of oxygen and carbon monoxide chemisorbed on a tungsten (111) crystal have been determined. The O⁺ ions released during ESD of adsorbed oxygen exhibit three-fold symmetric angular distributions in orientational registry with the W(111) substrate. The CO⁺ and O⁺ ions released during ESD of a monolayer of CO are desorbed normal to the (111) surface. Models for both oxygen and CO adsorption are discussed. The data for CO are consistent with adsorption of CO in “standing up” carbonyl structures in the virgin and α-CO binding states.     

Photoionization spectra of silver atoms adsorbed on the surface of a ZnS single crystal

We have used photostimulated flash luminescence to study deep electronic states arising when silver ions Ag⁺ are deposited under high vacuum onto the surface of a ZnS single crystal, followed by creation of the conditions for neutralization of the silver ions. The flux density of the silver ion beam was 10⁷ cm⁻²·sec⁻¹. We have observed the appearance of two types of deep electronic states with photoionization energies 1.60 eV and 1.80 eV, arising after depositing the silver ions onto the surface of the ZnS single crystal. We have hypothesized that there may be two different preferred sites for adsorption of silver atoms on the zinc sulfide surface. The corresponding photoionization spectra of the adsorbed silver atoms have maxima at 775 nm and 690 nm. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 3, pp. 335–338, May–June, 2006.     

Catalytic active sites on sputtered metal interfaces

By the use of Hartree-Fock-Slater (HFS) cluster calculations, the symmetry of adatom induced electronic states and their possible role in catalytic processes have been investigated. For iron adsorbed on a close packed iron single crystal surface we find an increased density of occupied “π” as well as “σ” states at the Fermi level. Simple group theoretical arguments give that the “π” states, which represent the highest occupied molecular orbitais (HOMO) will mix with the lowest unoccupied molecular orbital (LUMO) of CO, 2π¹, assuming CO bound normal to the surface in a terminal position with respect to the adatom. Such a system with an adsorbed atom on a flat surface is a model for a sputtered surface and these “π” states may thus explain the experimentally observed high rate of dissociation for CO on sputtered iron surfaces. A comparative study shows that no such increased density of states (DOS) is found when the Fe adatom is replaced by potassium. Finally for Cu adsorbed on Cu(111) only 4s derived “σ” states are introduced close to the Fermi level.     

Cl2 adsorption on MgO(001) surface supported sodium monolayers: a density functional theory study

The adsorption of Cl₂ Na monolayers supported on the MgO(001) surface has been studied by the density functional method using cluster models embedded in a large array of point charges (PCs). The value of PCs was determined by charge self-consistent technique. The results indicate that Na-promoted MgO(001) surface is an efficient catalyst toward Cl₂ adsorptive decomposition. Besides, it was found that the role of the MgO(001) surface is not passive, which is different from CO adsorption on MgO(001) surface supported Na metal monolayers. The analysis of band and projected density of states indicates that the electron transfer from the surface Mg 3s valence orbital and Na 3s valence orbital to the anti-bonding σ^∗ orbital of Cl₂ is the source of the Cl₂ bond weakening. This is also different from the CO adsorption on MgO(001) surface supported Na metal monolayers, where only the electrons from the Na valence orbital are transferred to the anti-bonding π^∗ orbital of adsorbed CO. Our study suggests that the essence of catalysis is different for CO and Cl₂ adsorption on Na metal monolayers supported an MgO(001) surface.     

Raman Spectroscopic Study of the Orientation of Polystyrene in a Stretched Film and in an Adsorbed Film

Abstract

Polarized Raman scattering spectra and surface enhanced Raman scattering spectra have been recorded from a thin film of a stretched polystyrene and from an adsorbed thin layer of polystyrene on silver surface, respectively. Comparison of intensities of the Raman line near 786 cm^?1 indicates that the aromatic rings are perpendicular to the surface in polystyrene which deposited onto silver from a very dilute solution.     

Quenching and enhancing of SERS of methyl orange after the addition of chlorine and nitrate anions

The influence of Cl⁻ and NO₃⁻ anions on surface enhanced Raman scattering (SERS) of methyl orange adsorbed on “chemical pure” silver colloids was studied. It was found that NO₃⁻ could give rise to a large enhancement of SERS of methyl orange, while Cl⁻ could obviously weaken the SERS intensity of this molecule. Both quenching and enhancing effects were discussed and compared with each other. It indicated the coadsorbed process of these adsorbed species, and different adsorption behaviors of the molecules on silver surface directly resulted in the difference. In addition, the results of TEM pictures and UV-visible spectral experiments have also confirmed the conclusion above.     

The electronic structure of CuCl: An “ab initio” Hartree-Fock SCF-MO study of the CuCl43− cluster

Results from restricted Hartree-Fock SCF-MO calculations on the CuCl₄^3? cluster occurring in solid CuCl are reported. The chemical bonding is discussed on the basis of a population analysis of the ground state orbitals. Calculations on the first ionized states show the Cu 3d electrons to be less tightly bound than the Cl 3p electrons in contrast to Koopmans' theorem predictions and in agreement with experiment. The high degree of localization of the 3d hole orbitals obtained is in conflict with earlier estimates of d-bond covalency. It is suggested that the “Ham effect” rather than covalency is responsible for the reduced spin orbit splitting that can be deduced from the observed exciton absorption. The potential surface for a Cu⁺ ion moving in the field of neighbouring Cl^? ions, has been determined from calculations on the CuCl₄^3? cluster in which the metal ion has been displaced towards a face, an edge or a vertex of the surrounding tetrahedron. The vibration frequency and the activation energy for the diffusion of Cu⁺ ions obtained are in fair agreement with the experimental data. These results support the viewpoint that the anomalous change in scattering intensity with temperature observed in X-ray and neutron diffraction studies is due to the presence of a substantial fraction of the Cu⁺ ions on interstitial lattice sites.     

X-ray and UV photoelectron-spectroscopic studies of pyridine adsorbed on evaporated nickel and palladium in the temperature range 140–385 k

The states of pyridine adsorbed on evaporated nickel and palladium films have been investigated as a function of temperature in the range 140–385 K by means of X-ray and UV photoelectron spectroscopy. At ～ 140 K, pyridine “N-bonded” on the metal surfaces gives C 1s and N 1s peaks whose binding energies are very close to those for condensed pyridine and “N-bonded” pyridine on pre-oxidized nickel. The high-lying valence orbitals, 2b₁ (π) and 1a₂ (π) + 7a₁ (n), of pyridine show shifts similar to those for the “N-bonded” molecule on pre-oxidized nickel. At ～ 290 K, “π-bonded” pyridine shows large shifts in the C 1s and N 1s peaks and in the high-lying valence orbitals, as observed for “π-bonded” benzene on nickel. The assignments of the adsorbed states are supported by work-function change data. A large proportion of pyridine converts from the “N-bonded” to the “π-bonded” form between 220 and 290 K. Formation of “α-pyridyl” is suggested at ～ 375 K on nickel.     

Thermal conductivity of gold and silver at high pressures

The thermal diffusivities of gold and silver have been measured under pressure up to 2.5 GPa at room temperature. From the measured data the pressure dependence of the thermal conductivity, λ, has been calculated. The values found for the pressure coefficient λ^?1$\text{δλ}\text{δP}$ were 3.9 × 10^?2GPa^?1 for gold and 4.0 × 10^?2 GP silver at atmospheric pressure. The results are compared to theoretical predictions of the pressure dependence and also to previous experimental results for copper and aluminium. For the noble metals, small angle or “vertical” scattering of electrons is shown to have a stronger volume dependence than “horizontal” scattering.     

金刚石延(111)面生长的第一性原理研究

利用密度泛函理论(DFT)对碳原子在镍(111)表面吸附结构进行了计算，得到了吸附能以及态密度 (density of state, DOS)分布，分析了吸附在镍(111)面的碳原子和金刚石(111)面的碳原子的分波态密度(PDOS)，结果表明吸附在镍表面的碳原子具有与金刚石表面碳原子相类似的电子结构特点，即两者都存在孤对的和成键的sp³杂化电子,进而发现吸附在镍表面的碳原子极易与金刚石表面相互作用形成稳定的类金刚石几何结构. 关键词： 密度泛函理论 化学吸附 电子结构 金刚石生长     

Optical spectra of (CdF2)0.9(InF3)0.1 semiconductor solid solutions

The differences in the optical spectra of CdF₂:In semiconductors with bistable DX centers (concentrated (CdF₂)_0.9(InF₃)_0.1 solid solutions) and “standard” samples with a lower impurity concentration used to record holograms are discussed. In contrast to the standard samples, in which complete decay of two-electron DX states and transfer of electrons to shallow donor levels may occur at low temperatures, long-term irradiation of a (CdF₂)_0.9(InF₃)_0.1 solid solution by UV or visible light leads to decay of no more than 20% deep centers. The experimental data and estimates of the statistical distribution of electrons over energy levels in this crystal give the total electron concentration, neutral donor concentration, and concentration of deep two-electron centers to be ～5 × 10¹⁸ cm^?3, ～9 × 10¹⁷ cm^?3, and more than 1 × 10²⁰ cm^?3, respectively. These estimates show that the majority of impurity ions are located in clusters and can form only deep two-electron states in CdF₂ crystals with a high indium content. In this case, In³⁺ ions in a limited concentration (In³⁺ (～9 × 10¹⁷ cm^?3) are statistically distributed in the “unperturbed” CdF₂ lattice and, as in low-concentrated samples, form DX centers, which possess both shallow hydrogen-like and deep two-electron states.     

Adsorption and coadsorption of carbon monoxide and hydrogen on Pd(111)

The adsorption and coadsorption of CO and H₂ have been studied by means of thermal desorption (TD) and electron stimulated desorption (ESD) at temperatures ranging from 250 to 400 K. Three CO TD states, labelled as β₂, β₁, and β₀ were detected after adsorption at 250 K. The population of β₂ and β₁ states which are the only ones observed upon adsorption at temperatures higher than 300 K was found to depend on adsorption temperature. The correlation between the binding states in the TD spectra and the ESD O⁺ and CO⁺ ions observed was discussed. Hydrogen is dissociatively adsorbed on Pd(111) and no ESD H⁺ signal was recorded following H₂ adsorption on a clean Pd surface. The presence of CO was found to cause an appearance of a H⁺ ESD signal, a decrease of hydrogen surface population and an arisement of a broad H₂ TD peak at about 450 K. An apparent influence of hydrogen on CO adsorption was detected at high hydrogen precoverages alone, leading to a decrease in the CO sticking coefficient and the relative population of CO β₂ state. The coadsorption results were interpreted assuming mutual interaction between CO and H at low and medium CO coverages, the “cooperative” species being responsible for the H⁺ ESD signal. Besides, the presence of CO was proved to favour hydrogen penetration into the bulk even at high CO coverage when H atoms were completely displaced from the surface.     

High-resolution electron energy-loss spectroscopy of CO on an Ni(110) surface

High-resolution vibrational electron energy-loss spectra of CO on an Ni(110) surface were studied at 300 K with the in-situ combination of LEED, Auger electron spectroscopy and work-function change measurement. The observed peaks are at 436 cm^?1, 1855 cm^?1 (shifting to 1944 cm^?1 with increasing coverage) and at 1960 cm^?1 (shifting to 2016 cm^?1 with increasing coverage). The experimental results indicate that CO is adsorbed non-dissociatively at all coverages. Three adsorbed states of CO have been found. At fractional CO coverages less than θ ~ 0.9 where the disordered adsorbed structure dominates, CO is adsorbed in two inequivalent sites (short- and long-bridge sites) at random with its axis oriented perpendicular to the surface. At high coverages (θ > 0.9) where the (2 × 1) structure develops, our results indicate that the adsorbed CO molecules may occupy the distorted long-bridge sites forming zig-zag chains which lie essentially in the troughs of the (110) surface.     

pH‐dependent surface‐enhanced Raman scattering observation of sulfanilamide on the silver surface

Monolayers of sulfanilamide on metallic surface can serve as an ideal model for understanding the interaction mechanism between the metal and the sulfanilamide molecule. In the present paper, the surface‐enhanced Raman scattering (SERS) technique was employed to obtain the SERS spectra of sulfanilamide monolayers formed on the silver surface under different pH values. Assignments of the spectra were carried out with the aid of density functional theory (DFT) calculations (BLYP/6‐311G). It can be found that the adsorption function of sulfanilamide on the silver surface was influenced by the pH value. The fully protonated sulfanilamide molecule adsorbed on the silver surface through N¹³H₂ group and the benzene ring anchored in a relatively perpendicular manner leading to N⁷H₂ and S¹⁰O₂ groups near the surface, while the completely deprotonated sulfanilamide molecule attached on the silver surface via N⁷H₂ and the benzene ring was perpendicular to, and the N¹³H₂ and S¹⁰O₂ groups were far from the silver surface. Copyright © 2009 John Wiley & Sons, Ltd.     

Surface-enhanced Raman spectroscopy of electrochemically characterized interfaces; potential dependence of Raman spectra for thiocyanate at silver electrodes

Surface-Enhanced Raman Spectra have been obtained for thiocyanate anions at silver electrodes following an oxidation-reduction cycle (ORC) as a function of electrode potential and electrolyte composition and compared with the extent of thiocyanate adsorption determined under the same conditions from differential capacitance-potential data. A spectrograph equipped with an optical multichannel analyzer (OMA) detector and a scanning spectrometer were used to make the Raman measurements. Spectra were obtained over the frequency range 100–2200 cm^?1, where all three normal vibrations, CN stretching (v_CN, 2090–2120 cm^?1), CS stretching (v_CN, 735 cm^?1), NCS angle bending (δ_NCS, 450 cm^?1) occur, along with a low frequency vibration attributed to a metal-ligand stretching mode (v_ml, 200–215 cm^?1) arising from a silver-sulfur surface bond. Both v_CN and v_ML decreased in frequency as well as intensity as the potential was made more negative in the region ?100 to ?700 mV versus Ag/AgCl for bulk thiocyanate concentrations of one millimolar and above, even though the thiocyanate surface concentration remained close to a monolayer throughout. By means of rapid time-resolved spectral measurements following potential steps using the OMA, the decrease of the intensity and frequency of the v_CN mode with increasing negative electrode potential was separated into a rapid “reversible” component and a slower “irreversible” decay. The latter component is attributed to the decay of Raman-active sites associated with the dissipation of metastable silver clusters formed during the ORC, that are prevented from rearranging at more positive potentials due to the presence of surrounding anionic adsorbate.     

Proprietes electriques du chlorure d'argent monocristallin et charge d'espace

Very high dielectric permittivity and polarisation in AgCl crystals are observed in d.c. and very low frequencies (from 10^?4 Hz to 100 KHz) with different electrodes (silver painting and solid chrome). The potential distribution is also studied with vibrating wire method.Near 100°C and for frequencies below 1 Hz, non-linear phenomenon appear for a.c. voltages greater than 0,1 V. When a.d.c. voltage is superposed, we observe three kinds of behaviour: for low voltages and low frequencies, adsorption predominates; for some volts, space charge appears and beyond surface states produce high permittivity.Shape of potential distribution and dielectric permittivity can be explained by space charge polarisation, adsorption of Ag⁺ ions at the electrodes and filling of surface states.     

The adsorption of ammonia on a Fe(110) single crystal surface studied by high resolution electron energy loss spectroscopy (EELS)

EELS spectra of ammonia adsorbed on a Fe(110) single crystal surface at 120 K reveal four different molecular adsorption states:1. At very low exposures (0.05 L) three vibrational losses at 345 cm^?1, 1170 and 3310 cm^?1 are observed which are attributed to the symmetric Fe-N stretching-, N-H₃ deformation and N-H₃ stretching modes of chemisorbed molecular ammonia, respectively. The observation of only three vibrational losses indicates an adsorption complex of high symmetry (C_3v).2. Further exposures up to 0.5 L cause the appearance of additional losses at 1450 cm^?1, 1640 cm^?1 and 3370 cm^?1. The latter two are interpreted as the degenerate NH₃ deformation and - stretching modes of molecularly adsorbed NH₃. The 1450 cm^?1 loss is a combination of the losses at 345 cm^?1 and 1105 cm^?1. The observation of 5 vibrational losses is consistent with an adsorption complex of C_s symmetry.3. In the exposure range from 0.5 to 2 L adsorption of molecular ammonia in a second layer is observed. This phase is characterized by a symmetric deformation mode at 1190 cm^?1 and by two additional very intense modes at 160 cm^?1 and 350 cm^?1 which are due to rotational and translational modes.4. Exposures above 2 L cause multilayer condensation of ammonia characterized by translational and rotational bands at 190 cm^?1, 415 cm^?1 and 520 cm^?1, and a symmetric deformation mode at 1090 cm^?1. A broad loss feature around 3300 cm^?1 is attributed to hydrogen bonding in the condensed layer.Thermal processing of a Fe(110) surface ammonia covered at 120 K leads to decomposition of the ammonia into hydrogen and nitrogen above 260 K. No vibrational modes due to adsorbed NH or HN₂ species were detected.     

Quantum-chemical simulation of adsorption of B+ ions on a SiO2/Si(100) interface

Quantum-chemical simulation of adsorption and migration of B⁺ ions on a SiO₂/Si(100) interface has been performed. The dependences of the total energy of the cluster-B⁺ ion system on the reaction coordinate and geometric and electronic characteristics of the equilibrium states of a cluster with an adsorbed boron ion have been calculated.     

Desorption kinetics and directional dependence of the surface diffusion of potassium on stepped W(100) surfaces

Using a surface ionisation ion microscope the desorption parameters and the diffusion constant of potassium were measured on stepped W(100) surfaces. The activation energy of ionic desorption as well as the corresponding prefactor do not depend on the step density; the mean adsorption lifetime τ can be expressed as τ=1.6×10^?14s exp(2.44 eV/kT).Whereas the surface diffusion of potassium on “flat” W(100) and on W(S)-[9(100)×(110)] was found to be isotropic, on W(S)- [5(100)×(110)] and W(S)-[3(100)×(110)] it occurs preferentially parallel to the step direction. The diffusion constant D_∥ for this direction has roughly the same value for all investigated surfaces: D_∥=7.8×10^?2 cm²s^?1 exp(?0.42 eV/kT). For the direction perpendicular to the steps D⊥ depends on the step density, whereby the activation energy as well as the prefactor increase with increasing step density.