Electronic properties of cesium ultrathin coatings on the Ga-rich GaAs(100) surface

The cesium submonolayer coatings on the Ga-rich GaAs(100) surface at different coverages have been investigated by threshold photoemission spectroscopy. The electronic spectra of surface states and the ion-ization energies are analyzed. At a cesium coverage of about one-half the monolayer, the spectrum exhibits two narrow adsorption-induced bands below the Fermi level. This indicates that cesium atoms interacting with gallium dimers occupy two nonequivalent positions. It is found that the gallium broken bonds are saturated at the cesium coverage of ～0.7 monolayer, and the adsorption bonding is predominantly covalent in character. At the coverages close to the monolayer, broad bands with energies of 1.9, 2.05, and 2.4 eV have been observed for the first time. These bands can be associated with the excitation of cesium islands, cesium clusters, and surface cesium plasmon, respectively. The results obtained suggest two adsorption stages characterized by the formation of strong and weak bonds.     

Molecular orbital study of the chemisorption of carbon monoxide on a tungsten (100) surface

The adsorption energies of carbon monoxide chemisorbed at various sites on a tungsten (100) surface have been calculated by extended Hückel molecular orbital theory (EHMO). The concept of a “surface molecule” in which CO is bonded to an array of tungsten atoms W_n has been employed. Dissociative adsorption in which C occupies a four-fold, five-coordination site and O occupies either a four- or two-fold site has been found to be the most stable form for CO on a W surface. Stable one-fold and two-fold sites of molecularly adsorbed CO have also been found in which the CO group is normal to the surface plane and the C atom is nearest the surface. Adsorption energies and molecular orbitals for the stable molecularly and dissociatively adsobred CO sites are compared with the experimental data on various types of adsorbed CO, i.e., virgin-, α-, and β-CO. Models are suggested for each of these adsorption types. The strongest bonding interactions occur between the CO 5σ orbital and the totally symmetric 5d and 6s orbitals of the W_n cluster. Possible mechanisms for conversion of molecularly adsorbed CO to dissociatively adsorbed CO are proposed and the corresponding activation energies are estimated.     

Translational heating of D(2) molecules thermally desorbed from Si(100) and Ge(100) surfaces

The translational energies of D(2) molecules thermally desorbed from the Si(100) and Ge(100) surfaces under a heating rate of 6 K/s have been measured. In contrast to the previous laser desorption study, results show a considerable translational heating; the observed translational temperature is about 3 times higher than the desorption temperature for both surfaces. This fact indicates that energy barriers for adsorption are present even in the desorption pathway. Detailed balance is applicable to the adsorption and desorption dynamics of hydrogen on the Si(100) surface.     

Adsorption of water molecule on (001) and (110) surfaces of MgH2

First principle calculations have been performed to explore the adsorption characteristics of water molecule on (001) and (110) surfaces of magnesium hydride. The stable adsorption configurations of water molecule on the surfaces of MgH₂ were identified by comparing the total energies of different adsorption states. The (110) surface shows a higher reactivity with H₂O molecule owing to the larger adsorption energy than the (001) surface, and the adsorption mechanisms of water molecule on the two surfaces were clarified from electronic structures. For both (001) and (110) surface adsorptions, the O p orbitals overlapped with the Mg s and p orbitals leading to interactions between O and Mg atoms and weakening the O–H bonds in water molecule. Due to the difference of the bonding strength between O and Mg atoms in the (001) and (110) surfaces, the adsorption energies and configurations of water molecule on the two surfaces are significantly different.     

The adsorption of hydrogen and the reaction of hydrogen with oxygen on Pt (100)

The adsorption of hydrogen on Pt (100) was investigated by utilizing LEED, Auger electron spectroscopy and flash desorption mass spectrometry. No new LEED structures were found during the adsorption of hydrogen. One desorption peak was detected by flash desorption with a desorption maximum at 160 °C. Quantitative evaluation of the flash desorption spectra yields a saturation coverage of 4.6 × 10¹⁴ atoms/cm² at room temperature with an initial sticking probability of 0.17. Second order desorption kinetics was observed and a desorption energy of 15–16 kcal/mole has been deduced. The shapes of the flash desorption spectra are discussed in terms of lateral interactions in the adsorbate and of the existence of two substates at the surface. The reaction between hydrogen and oxygen on Pt (100) has been investigated by monitoring the reaction product H₂O in a mass spectrometer. The temperature dependence of the reaction proved to be complex and different reaction mechanisms might be dominant at different temperatures. Oxygen excess in the gas phase inhibits the reaction by blocking reactive surface sites. At least two adsorption states of H₂O have to be considered on Pt (100). Desorption from the prevailing low energy state occurs below room temperature. Flash desorption spectra of strongly bound H₂O coadsorbed with hydrogen and oxygen have been obtained with desorption maxima at 190 °C and 340 °C.     

Hydrogen adsorption on Ni (100)

The adsorption of hydrogen on the (100) plane of nickel at room temperature has been investigated using the technique of flash desorption spectroscopy. It is shown that no variation in the adsorption enthalpy of 23.1 kcal/mole occurs during the chemical cleaning of the surface by repeated oxidation and reduction. The number of adsorption sites does however increase to 3.3×10¹⁴/cm² during this process. Determination of the partition functions of the adsorbed species and of the activated complex indicates that the hydrogen atoms are localised on specific adsorption sites but that greater liberty exists in the activated complex. Finally the experimental desorption spectra may be described using a model with a repulsive interaction of 400 cal/mole between nearest neighbours.     

Adsorption and desorption of ammonia,hydrogen, and nitrogen on ruthenium (0001)

The adsorption of ammonia, hydrogen, and nitrogen on a Ru(0001) surface have been investigated by Auger electron spectroscopy, low-energy electron diffraction, and thermal flash desorption. The adsorption of ammonia on Ru(0001) can be divided into a low temperature mode (100 K) and a higher temperature mode (300–500 K). For a crystal temperature of 100 K the ammonia adsorbs into two weakly bound molecular γ states with s = 0.2. The ammonia desorbs as NH₃ molecules with desorption energies of 0.32 and 0.46 eV. At 300–500 K adsorption occurs via an activated process with a low sticking probability (s ? 2 × 10^?4).This adsorption is accompanied by dissociation and formation of an apparent (2 × 2) LEED pattern. Hydrogen adsorbs readily (s = 0.4) on Ru(0001) at 100 K and desorbs with 2nd order kinetics in the temperature range 350–450 K. Nitrogen does not appreciably adsorb on Ru(0001) even at 100 K; maximum nitrogen coverage obtained was estimated to be <2% of a monolayer. Changes in the ammonia flash desorption spectra after hydrogen preadsorption at 100 K will be discussed.     

Adsorption of CH3Cl on clean and Cl-dosed Pd(100) surfaces

The adsorption of methyl chloride on a Pd(100) surface has been investigated by ultraviolet photoelectron spectroscopy (UPS), electron energy loss spectroscopy (in the electronic range, EELS), temperature-programmed desorption (TPD) and work function change. CH₃Cl adsorbs with high sticking probability at 80–100 K. UPS and TDS spectra suggest that the adsorption of CH₃Cl is molecular at 100 K, with a little distortion of the corresponding gas-phase molecular electronic structure. No dissociation of CH₃Cl was observed even up to 550 K. By means of TPD, we distinguished two adsorption states with desorption energies of 46.9 and 33.4 kJ/mol. The formation of a condensed layer at 105–110 K was also observed. Adsorption of CH₃Cl caused a significant work function decrease, Δ = −0.91 eV, indicating a dipole with positive end pointed away from the surface. The effects of electronegative additives, preadsorbed Cl and O were also examined. Preadsorbed Cl caused a slight destabilization of adsorbed CH₃Cl at lower concentration, prevented the adsorption of CH₃Cl at higher concentration and facilitated the formation of a condensed layer. No such effect was experienced in the presence of preadsorbed O.     

Thermal desorption of cyanogen from Pt(100)

Thermal desorption of cyanogen adsorbed on Pt(100) was studied by flash desorption mass spectrometry. By investigating the parent ion and all possible fragmentation products in the mass spectrometer during desorption it was concluded, that desorption takes place exclusively as molecular C₂N₂. Three desorption peaks were observed at 140, 410 and 480°C denoted as α, β₁ and β₂. The respective surface coverages at saturation were determined by quantitative evaluation of the flash desorption curves to be 2.0 ± 0.2 × 10¹⁴ and 5.5 ± 1.0 × 10¹⁴$\text{molecules}\text{cm}{}^2$ for the α and the β states, respectively. First order desorption kinetics was suggested by the coverage dependencé of the desorption spectra for both α and β states with desorption energies of 12 and 38–42 $\text{kcal}\text{mole}$, respectively. A large difference in the sticking probabilities of α and β states was observed with initial values of 0.06 (α) and 0.9 (β). Adsorption experiments at elevated temperatures led to the assumption, that α and β states coexist on the surface with no or very little interactions between them. The results are discussed in terms of different models for the adsorption states.     

Electron energy-loss spectra of clean and gas-covered Ni(100) surfaces

Electron energy-loss spectra have been measured on Ni(100) surfaces, clean and following oxygen and carbon monoxide adsorption, at primary energies of 40–300 eV. The observed peaks at 9.1, 14 and 19 eV in the clean-surface spectrum are ascribed to the bulk plasmon of the 4s electrons, the surface plasmon, and the bulk plasmon of the coupled 3d + 4s electron, respectively, and the weak but sharp peak at 33 eV is tentatively attributed to the localized many-body effect in the final state. Assignments of the loss structures on the gas-covered surfaces have been attempted.     

Electron energy loss spectrum of cyanogen on Pt (100)

Electron energy loss spectra for adsorbed cyanogen on Pt(100) are presented, and discussed in terms of possible models suggested by other techniques. Adsorbate induced loss features are found at 11 and 14 eV, and these are associated with levels below the Fermi level as observed in ultra-violet photoemission. As in the case of CO adsorption losses in the adsorbed phase occur at energies significantly larger than in the gas phase, indicating an upward shift of the final 2π¹ state due to mixing with metal orbitais. Thermal desorption studies of C₂N₂ on Pt clearly resolve α and β phases, but there is some controversy over whether the β phase involves mainly single CN units bonding to the metal, whether C₂N₂ is molecularly adsorbed, or whether paracyanogenlike structures form at the surface. The electron spectroscopic evidence is examined, and is shown on balance to support adsorption in some molecular form.     

Electron energy loss spectroscopy of the vibration modes of water on Ag(100) and Ag(115) surfaces and comparison to Au(100), Au(111) and Au(115)

Motivated by rather similar behavior of the Helmholtz capacitances of stepped Au(11n) and Ag(11n) electrodes we have extended a previous study on the vibration spectrum of water adsorbed at low temperatures on stepped gold surfaces to Ag(100), Ag(115) and Au(111) surfaces. On Ag(100) surfaces, the spectra show the presence of the typical H-bonded network of water molecules. The rather weak intensity, the absence of non-hydrogen bonded hydrogen atoms, the similarity to the infrared spectrum of ice crystallites, and the increase in the angular spread of the elastic peak are indicative of adsorption in form of three-dimensional clusters. This is stark contrast to Au(100) and Au(111) where the spectra match to a model involving stacks of water bilayers. The low coverage spectra on Ag(115) resemble the results on Au(115): A considerable fraction of the H-atoms remains in the non-H-bonded state and spectral features of water adsorbed at step-sites are identified. The first layer of water on Ag(115) surfaces should therefore have a similar structure as recently proposed in a theoretical study concerning water on Au(115). For larger doses, the experimental results on Ag(115) suggests the formation of three-dimensional clusters. This is contrary to Au(115) where the layered structure with a constant fraction of non-hydrogen-bonded H-atoms persists at higher doses.     

SrTiO3(100) step sites as catalytic centers for H2O dissociation

Features arising from surface Sr(Ti) atoms on the SrO(TiO₂) terraces of SrTiO₃ (100) have been resolved in core-level photoemission spectra, which provides new insights into the surface electronic structure and reactivity of transition metal oxides. The surface Sr 3d (Ti3s) features lie to lower (higher) initial energy of the bulk-derived peaks by ca. 1.0 eV (1.7 eV), being consistent with the expected enhancement of covalent bonding in the TiO₂-terrace surface. Step-sites, which connect the two types of terrace, are found to act as catalytic centers for H₂O dissociation.     

The adsorption of CO,O2, and H2 on Pt(100)-(5×20)

The adsorption/desorption characteristics of CO, O₂, and H₂ on the Pt(100)-(5 × 20) surface were examined using flash desorption spectroscopy. Subsequent to adsorption at 300 K, CO desorbed from the (5×20) surface in three peaks with binding energies of 28, 31.6 and 33 kcal gmol^?1. These states formed differently from those following adsorption on the Pt(100)-(1 × 1) surface, suggesting structural effects on adsorption. Oxygen could be readily adsorbed on the (5×20) surface at temperatures above 500 K and high O₂ fluxes up to coverages of $\text{2}\text{3}$ of a monolayer with a net sticking probability to ssaturation of ? 10^?3. Oxygen adsorption reconstructed the (5 × 20) surface, and several ordered LEED patterns were observed. Upon heating, oxygen desorbed from the surface in two peaks at 676 and 709 K; the lower temperature peak exhibited atrractive lateral interactions evidenced by autocatalytic desorption kinetics. Hydrogen was also found to reconstruct the (5 × 20) surface to the (1 × 1) structure, provided adsorption was performed at 200 K. For all three species, CO, O₂, and H₂, the surface returned to the (5 × 20) structure only after the adsorbates were completely desorbed from the surface.     

Photoelectron spectroscopic characterization of a-CO and b-CO on Fe(100)

The electronic differences between the low and the high coverage a-CO and b-CO adsorption state on Fe(100) [Benndorf et al., Surface Sci. 163 (1985) L675] were investigated with photoelectron spectroscopy using He I and He II radiation. The a- and b-CO adsorption states are sequentially filled with increasing coverage allowing to separate their contribution in the UPS spectra. The 1π + 5σ and the 4π signals from a- and b-CO show significant differences as well in the energy positions as in the intensity ratios.     

Mechanism of H2S molecule adsorption on the GaAs(100) surface: Ab initio quantum-chemical analysis

Ab initio quantum-chemical cluster calculations within the density-functional theory were carried out to study the mechanism of H₂S molecule adsorption on the gallium-rich surface of GaAs(100). It was shown that adsorption can occur in four stages: molecular adsorption; dissociative adsorption, during which an HS radical is adsorbed on a gallium atom comprising a dimer while the detached hydrogen atom is adsorbed on another surface atom of the semiconductor; hydrogen adatom migration between neighboring surface atoms of the semiconductor; and the formation of a Ga-S-Ga bridge bond and of a hydrogen molecule. The stationary-state energies and energy barriers to transitions between these states were determined. The conclusions drawn based on an analysis of calculated diagrams of the potential energy of the processes that occur are in good agreement with the experimental data available in the literature.     

Structure of the clean Ta(100) surface

The clean Ta(100) surface and some aspects of hydrogen adsorption have been studied by LEED and AES. The thorough examination of LEED patterns did not provide any evidence for an atomic reconstruction of the clean surface over the entire temperature range investigated, 150–600 K. The r-factor analysis used for comparison between measured and calculated I–V spectra yields a contraction of the topmost layer spacing of about 11% and an expansion of the second layer spacing of about 1% compared to the bulk value. The hydrogen adsorption does not induce any superstructures, but small hydrogen exposures lass then 1 L influence I–V spectra substantially.     

CO adsorption on alkali-metal covered Ni(100)

The effect of preadsorbed alkali metal atoms Na, K and Cs on CO adsorption on Ni(100) has been studied using Auger spectroscopy and thermal desorption. It was found that the presence of alkali metals causes an appearance of several more tightly bound states in the CO thermal desorption spectra. The observed difference in carbon and oxygen Auger peak line shape on a bare and alkali modified Ni(100) is indicative that the presence of alkali adatoms induces CO decomposition on the Ni(100) surface. The fraction of dissociated CO increases with the amount of alkali adatoms present. At the same overlayer coverage the dissociation probability increases in the sequence Na, K, Cs. A comparison of the strength of the promoting effect on CO dissociation with the changes in the surface electron density in the presence of alkali adatoms has shown that at low overlayer coverages the electronic factor plays a major role in explaining the action of the surface modificators.     

Selenium adsorption on Cs-covered Si(100) 2×1 surfaces

This report involves the study of Se adsorption on caesiated Si(100) 2×1 surfaces in ultra high vacuum (UHV) using low energy electron diffraction, Auger electron spectroscopy, thermal desorption spectroscopy and work function measurements. Selenium atoms on Cs/Si(100) 2×1 surface adsorb initially on uncaesiated portions of Si and subsequently on the Cs overlayer. The presence of Se increases the binding energy of Cs on Si(100). For Cs and Se coverages above 0.5 ml CsSe and Cs_xSe_ySi_z, compound formation was observed. The coadsorption of Se and Cs induces a high degree of surface disorder, while desorption most probably causes surface etching. The presence of Cs on Si(100) 2×1 surfaces prevents the diffusion of Se into the Si substrate and greatly suppresses the formation of SiSe₂ and SiSe₃, detected when Se is adsorbed on clean Si(100) 2×1 surfaces.