Penning ionization electron spectroscopy of H2O,D2O,H2S and SO2

Electron energy peak shifts and peak shapes were determined in the ionization of H₂O, D₂O, H₂S and SO₂ by Ne(³P₂) and He(2¹S, 2³S) metastable atoms. The shifts are large, especially in ionization of H₂O and D₂O into the ionic ground state and are probably mostly due to chemical interaction during the collision.In a previous paper the electron energy distribution curves for ionization of CO, HCl, HBr, N₂O, NO₂, CO₂, COS and CS₂ by helium, neon and argon metastables and the characteristics of this ionization were described¹. In this paper the series of triatomic molecules was extended to the molecules H₂O, D₂O, H₂S and SO₂. Because all these molecules have considerable dipole moments it could be expected that the peak shifts might be enhanced as compared with other triatomic molecules.     

[Co(CO2)n]+团簇的红外解离光谱实验和理论研究

本文利用红外光解离光谱研究了一价钴阳离子与二氧化碳之间的相互作用. 通过密度泛函理论计算得到[Co(CO₂)_n]⁺团簇的几何结构,并且模拟了它们的振动光谱与实验数值进行比较. 研究结果表明,在[Co(CO₂)_n]⁺(n=2∽6)团簇中,钴阳离子通过电四极矩静电作用以端点结合的方式与二氧化碳中的氧原子结合在一起. 团簇的红外光谱都集中在二氧化碳反对称伸缩的波数附近,并且随着团簇尺寸的变化出现蓝移,最后把[Co(CO₂)_n]⁺的红外光解离光谱与稀有气体贴附的[Co(CO₂)_n]⁺-Ar的红外光解离光谱进行了比较.     

Oxidation of CO on Fe2O3 model surfaces

Using first principles calculations based on a gradient corrected density functional formalism we show that Fe₂O₃ nano-particles with (1 0 0) and (0 0 0 1) surface orientations can oxidize CO to form CO₂ with or without the presence of O₂. However, depending on the surface orientation, the oxidation occurs through differing sequences. On the (1 0 0) surface, in the absence of O₂, two CO molecules are required for one CO oxidation in a concerted reaction while on a oxygen terminated (0 0 0 1) surface, a single CO molecule itself, without the aid of a second CO, can react with the lattice oxygen atoms to form CO₂. In the presence of O₂, the O vacancies created by an initial oxidation through lattice oxygen act as the favored sites for O₂ adsorption which can subsequently oxidize the incoming CO. Detailed reaction paths and the corresponding energetics for the proposed mechanisms are also studied.     

The adsorption of CO,H2, H2, CO2 and H2O on carburized and graphitized Ni(110)

A study of the adsorption/desorption behavior of CO, H₂O, CO₂ and H₂ on Ni(110)(4 × 5)-C and Ni(110)-graphite was made in order to assess the importance of desorption as a rate-limiting step for the decomposition of formic acid and to identify available reaction channels for the decomposition. The carbide surface adsorbed CO and H₂O in amounts comparable to the clean surface, whereas this surface, unlike clean Ni(110), did not appreciably adsorb H₂. The binding energy of CO on the carbide was coverage sensitive, decreasing from 21 to 12 $\text{kcal}\text{mol}$ as the CO coverage approached 1.1 × 10¹⁵ molecules cm^?2 at 200K. The initial sticking probability and maximum coverage of CO on the carbide surface were close to that observed for clean Ni(110). The amount of H₂, CO, CO₂ and H₂O adsorbed on the graphitized surface was insignificant relative to the clean surface. The kinetics of adsorption/desorption of the states observed are discussed.     

Interaction of O2, CO2, CO,C2H4 and C2H4O with Ag(110)

The interaction of O₂, CO₂, CO, C₂H₄ AND C₂H₄O with Ag(110) has been studied by low energy electron diffraction (LEED), temperature programmed desorption (TPD) and electron energy loss spectroscopy (EELS). For adsorbed oxygen the EELS and TPD signals are measured as a function of coverage (θ). Up to θ = 0.25 the EELS signal is proportional to coverage; above 0.25 evidence is found for dipole-dipole interaction as the EELS signal is no longer proportional to coverage. The TPD signal is not directly proportional to the oxygen coverage, which is explained by diffusion of part of the adsorbed oxygen into the bulk. Oxygen has been adsorbed both at pressures of less than 10^-4 Pa in an ultrahigh vacuum chamber and at pressures up to 10³ Pa in a preparation chamber. After desorption at 10³ Pa a new type of weakly bound subsurface oxygen is identified, which can be transferred to the surface by heating the crystal to 470 K. CO₂ is not adsorbed as such on clean silver at 300 K. However, it is adsorbed in the form of a carbonate ion if the surface is first exposed to oxygen. If the crystal is heated this complex decomposes into O_ad and CO₂ with an activation energy of 27 kcal/mol(1 kcal = 4.187 kJ). Up to an oxygen coverage of 0.25 one CO₂ molecule is adsorbed per two oxygen atoms on the surface. At higher oxygen coverages the amount of CO₂ adsorbed becomes smaller. CO readily reacts with O_ad at room temperature to form CO₂. This reaction has been used to measure the number of O atoms present on the surface at 300 K relative to the amount of CO₂ that is adsorbed at 300 K by the formation of a carbonate ion. Weakly bound subsurface oxygen does not react with CO at 300 K. Adsorption of C₂H₄O at 110 K is promoted by the presence of atomic oxygen. The activation energy for desorption of C₂H₄O from clean silver is ～ 9 kcal/mol, whereas on the oxygen-precovered surface two states are found with activation energies of 8.5 and 12.5 kcal/mol. The results are discussed in terms of the mechanism of ethylene epoxidation over unpromoted and unmoderated silver.     

Methanol decomposition on the β-Ga2O3 (1 0 0) surface: A DFT approach

Density functional theory (DFT) cluster model calculations on methanol reactions on the β-Ga₂O₃ (1 0 0) surface have been realized. β-Ga₂O₃ structure has tetrahedral and octahedral ions and the results of gallia-methanol interaction are different depending on the local surface chemical composition. The surface without oxygen vacancies is very reactive and produces the methanol molecule decomposition. The unsaturated surface oxygen atoms strongly oxidize the methanol molecule. CO₂ and H₂O molecules are produced when methanol reacts with a free oxygen vacancy surface on octahedral gallium sites. On the other hand, H₂CO is found after the reaction of this molecule with a free O vacancy surface on tetrahedral gallium sites. A weak interaction between the remaining CO₂ molecule and the oxide surface was found, being this molecule easy to desorb. Otherwise, H₂CO has a stronger surface bond and it could suffer a later oxidation.     

Infrared spectra and stability of CO and H2O sorption over Ag-exchanged ZSM-5 zeolite: DFT study

The infrared spectra and stability of CO and H₂O sorption over Ag-exchanged ZSM-5 zeolite were investigated by using density function theory (DFT). The changes of NBO charge show that the electron transfers from CO molecule to the Ag⁺ cation to form an σ-bond, and it accompanies by the back donation of d-electrons from Ag⁺ cation to the CO (π*) orbital as one and two CO molecules are adsorbed on Ag-ZSM-5. The free energy changes ΔG, −5.55 kcal/mol and 6.52 kcal/mol for one and two CO molecules, illustrate that the Ag⁺(CO)₂ complex is unstable at the room temperature. The vibration frequency of C-O stretching of one CO molecule bonded to Ag⁺ ion at 2211 cm⁻¹ is in good agreement with the experimental results. The calculated C-O symmetric and antisymmetric stretching frequencies in the Ag⁺(CO)₂ complex shift to 2231 cm⁻¹ and 2205 cm⁻¹ when the second CO molecule is adsorbed. The calculated C-O stretching frequency in CO-Ag-ZSM-5-H₂O complex shifts to 2199 cm⁻¹, the symmetric and antisymmetric O-H stretching frequencies are 3390 cm⁻¹ and 3869 cm⁻¹, respectively. The Gibbs free energy change (ΔGH₂O) is −6.58 kcal/mol as a H₂O molecule is adsorbed on CO-Ag-ZSM-5 complex at 298 K. The results show that CO-Ag-ZSM-5-H₂O complex is more stable at room temperature.     

The adsorption of CO2 and CO on Ca and CaO films studied with MIES, UPS and XPS

Metastable Induced Electron Spectroscopy (MIES), Ultraviolet Photoelectron Spectroscopy (UPS), and X-ray Photoelectron Spectroscopy (XPS) are employed to study the adsorption of CO₂ and CO on Ca and CaO films. Ca films are prepared by evaporation of Ca onto clean Si(1 0 0) substrates. CaO films are produced by Ca evaporation in an oxygen atmosphere at a substrate temperature of 670 K. CO₂ interaction with the Ca films is initiated by dissociation of the impinging molecules leading to the formation of Ca-O bonds. These Ca-O bonds are subsequently consumed in the formation of a closed CaCO₃ layer on top of the surface. CO interaction with the Ca surfaces also leads to the dissociation of the molecule and the formation of Ca-O bonds. We find evidence for the subsequent formation of complexes on top of the surface. On CaO surfaces, both CO₂ and CO lead to the formation of a closed CaCO₃ top layer, though displaying very different reaction rates.     

Far-infrared absorption intensities of H2O and D2O in C6H6

Far-i.r. absorption intensities have been measured for H₂O and D₂O in C₆H₆ solutions. Beer's law plots were found to be nonlinear. From the plots, the equilibrium constants of dimer formation in benzene were estimated to be 2.4M^-1 and 3.3M^-1 for H₂O and D₂O at 20°C, respectively. Based on Onsager's reaction field and including explicitly the effect of differences in molecular size between solute and solvent molecules, the internal moment of a water molecule and the volume ratio of a molecule to a cavity were estimated from the integrated absorption intensity of a D₂O monomer in C₆H₆ as 1.98 D and 0.7, respectively     

Evidence for Eley-Rideal abstraction mechanism in reactive ion scattering of Cs from Pt(1 1 1) adsorbed with CO and CO2

We studied the reactive ion scattering (RIS) of Cs⁺ from a Pt(1 1 1) surface adsorbed with CO and CO₂ leading to the emission of CsCO⁺ and . The RIS products were measured as functions of adsorbate coverage and ion incidence energy for the range of 10-60 eV. The yield and cross-section for the RIS processes were extracted from these measurements. The RIS cross-section is higher for weakly adsorbed CO₂ than for more strongly bound CO. The RIS energy-dependence shows a maximum at 15-20 eV and a decrease at higher energy. These observations provide evidence for the theoretically proposed mechanism of RIS, in which a slow Cs⁺ picks up an adsorbate in an Eley-Rideal abstraction reaction.     

Reaction mechanism for CO oxidation on Cu(3 1 1): A density functional theory study

The microscopic reaction mechanism for CO oxidation on Cu(3 1 1) surface has been investigated by means of comprehensive density functional theory (DFT) calculations. The elementary steps studied include O₂ adsorption and dissociation, dissociated O atom adsorption and diffusion, as well as CO adsorption and oxidation on the metal. Our results reveal that O₂ is considerably reactive on the Cu(3 1 1) surface and will spontaneously dissociate at several adsorption states, which process are highly dependent on the orientation and site of the adsorbed oxygen molecule. The dissociated O atom may likely diffuse via inner terrace sites or from a terrace site to a step site due to the low barriers. Furthermore, we find that the energetically most favorable site for CO molecule on Cu(3 1 1) is the step edge site. According to our calculations, the reaction barrier of CO + O → CO₂ is about 0.3 eV lower in energy than that of CO + O₂ → CO₂ + O, suggesting the former mechanism play a main role in CO oxidation on the Cu(3 1 1) surface.     

The chemisorption of CO,CO2, C2H2, C2H4, H2 and NH3 on the clean Fe(100) and (111) crystal surfaces

The chemisorption of small molecules (CO, CO₂, C₂H₂, C₂H₄, H₂ and NH₃) has been studied on the clean Fe(110) and (111) crystal faces by low-energy electron diffraction (LEED) and thermal desorption. C₂H₄ and C₂H₂ yield the same sequence of surface structures that change with temperature and crystal orientation. CO and CO₂ chemisorption similarly results in the formation of the same types of surface structures that change with surface temperature and crystal orientation. Ammonia forms several ordered surface structures on both iron crystal faces. All of the molecules decompose as a function of temperature on the iron surfaces as indicated by the Auger and thermal desorption spectra.     

Adsorption of CO and C2H4 on Rh-loaded thin-film dysprosium oxide

A dysprosium oxide thin film was deposited on Ru(0 0 0 1) by vapor depositing Dy in 2 × 10⁻⁷ torr O₂ while the Ru was at 700 K. The film was ca. 5 nm thick and produced a p(1.4 × 1.4) LEED pattern relative to the Ru(0 0 0 1) substrate. The adsorption and reaction of CO and C₂H₄ adsorbed on Rh supported on the Dy₂O₃ film were studied by TPD and SXPS. The CO initially reacted with loosely bound oxygen in the substrate to produce CO₂. After the loosely bound oxygen was removed, the CO adsorbed non-dissociatively in a manner similar to what is seen on Rh(1 1 1). C₂H₄ adsorbed on the Rh particles and underwent progressive dehydrogenation to produce H₂ during TPD. The C from the C₂H₄ reacted with the O in Dy₂O₃ to produce CO. CO dissociation on the Rh particles could be promoted by treating the Dy₂O₃ with C₂H₄ before CO exposure.     

Sputtering of Ta2O5 by Ar+ ions at energies below 1 keV

The sputtering of anodically formed Ta₂O₅ layers of about 3500 Å thickness has been studied by Sputtered Neutral Mass Spectroscopy (SNMS). For perpendicular bombardment with Ar⁺ ions up to 900 eV the flux of ejected neutral particles is found to consist almost exclusively of metal atoms Ta and Oxide specific molecules TaO and TaO₂ with intensity ratios in the order 1 : 1 : 10^?1. From depth profiling measurements with SNMS, and from the intensity ratios in the SNMS spectra the total sputtering yield of Ta₂O₅ and the partial yields of Ta, TaO and of oxygen have been determined for normally incident Ar⁺ ions of 100 to 600 eV. After an initial increase the TaO intensity in the SNMS spectra remains constant during the sputter removal of the whole layer. A simple model is derived by which the preferred emission of TaO molecules, and the initial increase of the TaO intensity is referred to ion induced variations of the surface stoichiometry of Ta₂O₅. For optimum TaO production the model predicts equal atomic surface concentrations of Ta and O.     

Velocity dependence of the chemi-ionization of H2O and D2O on impact of 21S and 23S helium atoms

The velocity dependence for the ionization of H₂O and D₂O to form H₂O⁺ and D₂O⁺ in collisions with both 2³S and 2¹S metastable helium atoms has been measured in a crossed molecular beam apparatus using a mechanical velocity-selector on the metastable beam. The cross-sections are found to be proportional to the —n power of the relative collision energy, with n ? 0.4 for both metastable atoms in both gases. The branching ratios H₂O⁺/OH⁺ and D₂O⁺/OD⁺ were both found to be 4.3 for both metastable helium atoms, and to be independent of the relative collision energy.     

A density functional theory study on the adsorption of CO and O2 on Cu-terminated Cu2O （111） surface

The adsorptions of CO and 02 molecules individually on the stoichiometric Cu-terminatcd Cu20 （111） surface are investigated by first-principles calculations on the basis of the density functional theory. The calculated results indicate that the CO molecule preferably coordinates to the Cu2 site through its C atom with an adsorption energy of-1.69 eV, whereas the 02 molecule is most stably adsorbed in a tilt type with one O atom coordinating to the Cu2 site and the other O atom coordinating to the Cul site, and has an adsorption energy of -1.97 eV. From the analysis of density of states, it is observed that Cu 3d transfers electrons to 2π orbital of the CO molecule and the highest occupied 5σ orbital of the CO molecule transfers electrons to the substrate. The sharp band of Cu 4s is delocalized when compared to that before the CO molecule adsorption, and overlaps substantially with bands of the adsorbed CO molecule. There is a broadening of the 2π orbital of the 02 molecule because of its overlapping with the Cu 3d orbital, indicating that strong 3d-2π interactions are involved in the chemisorption of the 02 molecule on the surface.     

Study of the luminescence of H2O and D2O ices induced by charged-particle bombardment

We measured the optical emission of H₂O and D₂O ices in visible region (300-500 nm) induced by energetic hydrogen ions (H⁺, H₂⁺, and H₃⁺) irradiation. Our analysis of the data of ion-stimulated luminescence (ISL) shows that all spectra of ISL emission are identical, independent of projectile. We show that all lines in the ISL emission spectrum may be assigned to decays from excited particles and/or fragments of H, H₂, OH, and H₂O. From the independence of emission spectrum on projectile we conclude that the final process causing the emissions may be attributed to the interaction between H⁺ (and/or H) and the water molecules.     

Composition depth profiles of Bi3.15Nd0.85Ti3O12 thin films studied by X-ray photoelectron spectroscopy

In the present work, X-ray photoelectron spectroscopy (XPS) was used to investigate the composition depth profiles of Bi_3.15Nd_0.85Ti₃O₁₂ (BNT) ferroelectric thin film, which was prepared on Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by chemical solution deposition (CSD). It is shown that there are three distinct regions formed in BNT film, which are surface layer, bulk film and interface layer. The surface of film is found to consist of one outermost Bi-rich region. High resolution spectra of the O 1s peak in the surface can be decomposed into two components of metallic oxide oxygen and surface adsorbed oxygen. The distribution of component elements is nearly uniform within the bulk film. In the bulk film, high resolution XPS spectra of O 1s, Bi 4f, Nd 3d, Ti 2p are in agreement with the element chemical states of the BNT system. The interfacial layer is formed through the interdiffusion between the BNT film and Pt electrode. In addition, the Ar⁺-ion sputtering changes lots of Bi³⁺ ions into Bi⁰ due to weak Bi-O bond and high etching energy.     

Ejection of H2O,O2, H2 and H from water ice by 0.5–6 keV H+ and Ne+ ion bombardment

The ejection of H₂O, O₂, H₂ and H from water ice at 30–140 K, bombarded by 0.5–6 keV H⁺ and Ne⁺ was studied experimentally. Neon ions in this energy range deposit their energy in the ice by nuclear collisions, whereas with protons of 0.5 to 6 keV the energy deposition mechanism shifts gradually from predominantly nuclear collisions to predominantly electronic processes. The existing theory of nuclear sputtering predicts very well the yield of ejected water molecules and the experimental results in the region of electronic processes agree well with the experimental results of Lanzerotti, Brown and Johnson. However, the major mass loss from water by ion bombardment is via the ejection of O₂, H₂ and H atoms, which exceed the ejection of water molecules. O₂ and H₂ production is markedly enhanced at temperatures exceeding ~100 K, whereas H₂O and H production are temperature independent, suggesting that O₂ and H₂ are produced in the bulk of the ice whereas H₂O and H atoms are ejected from the surface or near surface layers.     

Vibrational study of H3OUO2PO4 · 3 H2O (HUP) and related compounds. phase transitions and conductivity mechanisms: part I,KUO2PO4 · 3 H2O (KUP)

Infrared and Raman spectra of polycrystalline KUO₂PO₄ · 3 H₂O (KUP) and its isotopic derivatives KUO₂P¹⁸O₄ · 3 H₂O and KUO₂PO₄ · 3 D₂O have been investigated in the 4000-10-cm^?1 range at different temperatures. An assignment of the bands in terms of UO₂, PO₄ and H₂O vibrations has been proposed. Combined differential scanning calorimetry and spectroscopic data show two diffuse phase transitions near 130 and 230 K. Comparison of the vibrational spectra of phase I at 300 K and phase IV at 100 K indicates that ordering of the water molecules with subsequent ordering of PO₄ tetrahedra on a site with lower symmetry appears to be the main mechanism responsible for the phase transformation. All the six O-H distances of water molecules in phase IV are found to be crystallographically nonequivalent. Conducting ion frequencies and the corresponding force constants have been determined for the analogous compounds MUP with M = K⁺, Na⁺, Ag⁺, NH⁺₄, Tl⁺ and H₃O⁺ and compared with other properties of these ionic conductors. Conductivity mechanisms in these materials are discussed.