BaxOy小团簇修饰Ru(0001)表面的结构稳定性和氮分子吸附性质

为了说明钡助剂的存在形式, 本文采用第一性原理方法研究了Ba_xO_y小团簇修饰Ru(0001)表面的结构稳定性和氮分子吸附性质. 基于总能的热力学分析发现, 在实验条件下(500 K, P_H2O/P_H2<10^-3), Ba₂O团簇比BaO₂, BaO, Ba和O等团簇(原子)更加稳定. 这证实含有金属性钡原子的团簇也是氧化钡助剂可能的工作状态. 表面电荷差分密度说明Ba₂O团簇的氧和钡原子与衬底的作用不同. 不过Ba₂O团簇氧和钡原子附近的氮分子吸附行为相似, Ba₂O团簇增强了氮分子和衬底的相互作用. Ba₂O团簇氧和钡原子附近的氮分子吸附能分别为0.78 和0.88 eV, 均大于清洁表面的0.67 eV. 氮分子间距和氮分子的拉伸振动频率都表明Ba₂O团簇在一定程度上活化了吸附氮分子. Ba₂O团簇氧和钡原子附近的N–N键长分别为0.117和0.116 nm, 大于清洁表面的0.114 nm. 氧和钡原子附近氮分子的拉伸振动频率分别为 1888 和1985 cm^-1, 小于清洁表面的2193 cm^-1. 电荷差分密度的计算结果说明, 削弱作用主要来自于Ba₂O团簇中钡离子和氮分子间的静电作用. 两者间的静电作用增加了氮分子π 反键轨道的占据数, 促进了氮分子极化, 从而削弱氮分子键.     

Condensed water in superfluid He-II

It was found that when ⁴He gas containing water vapor as an impurity condenses on the surface of superfluid He-II cooled to ∼ 1.4 K, semitransparent clouds (icebergs) form in the volume of a glass cell filled with He-II below the He-II surface. The form of the icebergs extracted from the superfluid liquid remains virtually unchanged on heating up to ∼ 1.8 K. In the temperature range 1.8–2.2 K the thermometers register sharp temperature jumps, which are accompanied by jumps in the gas pressure in the cell and a repeated decrease, by more than two orders of magnitude, in the total volume of the condensate, i.e., the water content in the volume of an iceberg does not exceed 10²⁰H₂O molecules per 1 cm³. It can be inferred that porous icebergs, permeated with superfluid liquid and containing cores consisting of small clusters surrounded by a layer of solidified helium, form in the volume of He-II as the gas mixture condenses. Pis’ma Zh. éksp. Teor. Fiz. 70, No. 11, 744–748 (10 December 1999)     

Adsorption of CO, CO2 and NO molecules on a BaTiO3 (0 0 1) surface

Since the development of Scanning Tunnelling Microscopy (STM) technique, considerable attention has been devoted to various molecules adsorbed on various surfaces. Also, a new concept emerged with molecules on surfaces considered as nano machines by themselves. In this context, a thorough knowledge of surfaces and adsorbed molecules at an atomic scale are thus particularly invaluable. The present work describes the first Density Functional Theory (DFT) study of adsorption of CO, CO₂ and NO molecules on a BaTiO₃ surface following a first preliminary calculation of O and O₂ adsorption on the same surface. In the previously considered work, we found that a (0 0 1) surface with BaO termination is more stable than the one with TiO₂-termination. Consequently, we extended our study to CO, CO₂ and NO molecules adsorbed on a (0 0 1) surface with BaO termination. The present calculation was performed on a (1 × 1) cell with one monolayer of adsorbed molecules. Especially, a series of cases implying CO molecules adsorbed in various geometrical configurations has been examined. The corresponding adsorption energy varies in the range of −0.17 to −0.10 eV. The adsorption energy of a CO₂ molecule directly located above an O surface atom (called O_s) is of the order of −0.18 eV. The O-C distance length is then 1.24 Å and the O-C-O and O-C-O_s angles are 134.0° and 113.0°, respectively. For NO adsorption, the most important induced structural changes are the followings: (i) the N-O bond is broken when a NO molecule is absorbed on a Ba-O_s bridge site. In that case, N and O atoms are located above an O and a Ba surface atom, respectively, whereas the O-Ba-O_s and N-O_s-Ba angles are 106.5° and 63.0°, respectively. The N-O distance is as large as 2.58 Å and the adsorption energy is as much as −2.28 eV. (ii) In the second stable position, the NO molecule has its N atom adsorbed above an O_s atom, the N-O axis being tilted toward the Ba atom. The N-O_s-Ba angle is then 41.1° while the adsorption energy is only −0.10 eV. At last, the local densities of states around C, O as well as N atoms of the considered adsorbed molecules have also been discussed.     

Diffusivity of a two-dimensional lattice fluid: CH4 adsorbed on MgO(100)

The diffusive motions of a 0.8 layer of CH₄ adsorbed on MgO(100) are measured at 72, 88 and 97 K by quasi-elastic neutron scattering. It is shown that at 72 K the methane film is solid and its molecules perform an isotropic rotational motion. At 88 and 97 K, the adsorbed layer is in a two-dimensional fluid state in which the molecules jump between equidistant (4.21 Å) lattice sites of the MgO surface. The mean residence time has been determined ( ∼ 1 × 10 ⁻¹⁰ s at 88 K and ∼ 4 × 10⁻¹¹ s at 97 K). The corresponding translational diffusion coefficients are ∼ 5 × 10⁻⁶ cm² s⁻¹ at 88 K and 12 × 10⁻⁶ cm² s⁻¹ at 97 K. The diffusivity of this lattice fluid is compared to that of the same molecules adsorbed on graphite (0001) previously reported. The reduced mobility observed in the case of CH₄/MgO(100) is related to the important depth of the potential wells on the MgO(100) surface.     

Adsorption of oxygen on W(110): II. The high coverage range

The structure and composition of the interaction layer between oxygen and a W(110) surface for oxygen coverages θ above 0.5 monolayers is studied with LEED, AES, thermal desorption and work function change measurements. Oxygen is adsorbed by depositing WO₂ followed by annealing. The results are interpreted in terms of a topmost layer consisting only of oxygen atoms followed by the formation of isolated three-dimensional WO₃ crystals after saturation of the two-dimensional oxidation layer at 15 × 10¹⁴ O atoms cm^?2. All available experimental evidence is compatible with this interpretation.     

Vibrational properties of the adsorbed monolayer on face-centered cubic crystals

Calculations of mean-square displacements 〈u²〉 of the atoms in adsorbed monolayers on fcc crystals are presented and compared with LEED experimental results. This text is restricted to the case of a C(2 × 2) adsorbed layer on a (100) surface [experimental case of Ni(100) with adsorbed sulfur, sodium, cesium or oxygen]. 〈u²〉's perpendicular to and parallel to a (100) surface are calculated for the adsorbed atoms and the atoms of the first surface layer of the crystal. The values obtained are compared with those for a clean (100) surface and the volume of the crystal. Every possibility for force constants between adsorbate and substrate atoms is examined. It is shown that the measurement of 〈u²〉 perpendicular to the (100) surface yields the adsorbate-substrate force constants and that 〈u²〉 parallel to the (100) surface yields the adsorbate-adsorbate force constants.     

Water adsorption on the Be(0001) surface: from monomer to trimer adsorption

In this paper, the density functional theory has been used to perform a comparative theoretical study of water monomer, dimer, trimer, and bilayer adsorptions on the Be(0001) surface. In our calculations, the adsorbed water molecules are energetically favoured adsorbed on the atop sites, and the dimer adsorption is found to be the most stable with a peak adsorption energy of ～437 meV. Further analyses have revealed that the essential bonding interaction between the water monomer and the metal substrate is the hybridization of the water 3a₁-like molecular orbital with the (s, p_z) orbitals of the surface beryllium atoms. While in the case of the water dimer adsorption, the 1b₁-like orbital of the H₂O molecule plays a dominant role.     

SERS and XPS observation of the adsorption behavior of NO and NO2 on a silver powder surface

The influence of H₂O on the adsorption behavior of NO or NO₂ on a silver powder surface was studied by SERS and XPS at room temperature. Water vapor was found to be responsible for the adsorption of NO on the silver powder surface. When surface species such as Ag₂O are present on the surface, some of the NO₂ molecules are adsorbed on the surface species to produce NO^-₃, whereas NO molecules are adsorbed on a different site to produce NO^-₂.     

The bonding of water molecules to platinum surfaces

Using high resolution electron energy loss spectroscopy in ultra-high vacuum we have studied the vibrational spectrum of submonolayer and multilayer quantities of water adsorbed on platinum (100) surfaces. For adsorbed multilayers the spectrum resembles the spectrum of ice I. For submonolayer quantities of H₂O we find three different OH stretching vibrations, 2850, 3380, and 3670 cm^?1. The highest frequency is attributed to free OH groups. The vibration around 3380 cm^?1 indicates H bonding between oxygen atoms. It is therefore concluded that the water molecules cluster even at low coverage. The lowest OH stretching frequency is attributed to H bonding to platinum. We find also evidence for additional oxygen lone pair orbital bonding to the surface which disappears however when the first monolayer is completed. The relation to currently considered models in electrochemistry of aqueous solutions is discussed.     

The adsorption and reaction of H2O on clean and oxygen covered Ag(110)

The adsorption and reaction of water on clean and oxygen covered Ag(110) surfaces has been studied with high resolution electron energy loss (EELS), temperature programmed desorption (TPD), and X-ray photoelectron (XPS) spectroscopy. Non-dissociative adsorption of water was observed on both surfaces at 100 K. The vibrational spectra of these adsorbates at 100 K compared favorably to infrared absorption spectra of ice Ih. Both surfaces exhibited a desorption state at 170 K representative of multilayer H₂O desorption. Desorption states due to hydrogen-bonded and non-hydrogen-bonded water molecules at 200 and 240 K, respectively, were observed from the surface predosed with oxygen. EEL spectra of the 240 K state showed features at 550 and 840 cm^?1 which were assigned to restricted rotations of the adsorbed molecule. The reaction of adsorbed H₂O with pre-adsorbed oxygen to produce adsorbed hydroxyl groups was observed by EELS in the temperature range 205 to 255 K. The adsorbed hydroxyl groups recombined at 320 K to yield both a TPD water peak at 320 K and adsorbed atomic oxygen. XPS results indicated that water reacted completely with adsorbed oxygen to form OH with no residual atomic oxygen. Solvation between hydrogen-bonded H₂O molecules and hydroxyl groups is proposed to account for the results of this work and earlier work showing complete isotopic exchange between H₂¹⁶O_(a) and ¹⁸O_(a).     

Simultaneous and sequential adsorption of deuterium and nitrous oxide by rhenium

The addition of nitrous oxide to a stream of deuterium passing over a rhenium filament reduced the initial sticking probability of the latter gas from 0.24 to 0.09 when the proportion of N₂O exceeded 40%. For the addition of deuterium to nitrous oxide the equivalent figures were 0.45 and 0.30 when deuterium exceeded 30% of the gas phase. These results are attributed to a competition between the two gases for places in the precursor state on the surface. The replacement of adsorbed deuterium from a saturated layer by the oxygen atom of nitrous oxide proceeded initially with a high probability, 0.27, at room temperature and with each oxygen atom replacing one deuterium atom. However, the reaction was incomplete, about 2 × 10¹⁴ atoms cm^?2 of deuterium remaining on the surface. It is suggested that kinetic rather than thermodynamic factors are responsible for the incomplete reaction, possibly as the result of a high activation energy for the migration of deuterium atoms over an oxygenated rhenium surface.     

Proton spin relaxation of molecules adsorbed in NaY and NaPtY zeolite; The influence of adsorbed water on the distribution of atomic platinum

The longitudinal proton spin relaxation time T₁ of molecules adsorbed in commercial zeolites is predominantly caused by paramagnetic impurities, typically of the order of 0.1 wt% of iron. If only 1 wt% of platinum is introduced into the zeolite (as [Pt(NH₃)₄]²⁺), T₁ of water is enhanced up to one order of magnitude, as was shown in a preceding paper. The reason for this effect is that, under suitable thermal pretreatment of the Pt-exchanged zeolite, the Pt²⁺ ions are reduced by the ammonia to atomic platinum and part of the Pt atoms migrate preferentially to Fe³⁺ ions. Thus, Fe³⁺ ions, controlling T₁, are covered and up to 90% of paramagnetic sites for water is occupied by Pt atoms. In this paper, it is shown that Pt atoms preferentially migrate to Fe³⁺ ions only under the influence of water and that, therefore, various adsorbed organic molecules do not show the enhancement of T₁, unless the NaPtY zeolite is suitably pretreated with water before the organic molecules are adsorbed.     

Isotope exchange studies of the oxidation and reduction of SrTiO3 single crystal surfaces by water and hydrogen

Thermal desorption studies of chemisorbed D₂ and D₂O on a reduced SrTiO₃(111) surface reveal that D₂ causes the reduction of the crystal, whereas D₂O causes its oxidation. Thermal desorption of H₂¹⁸O indicates that there is a 15% exchange between the oxygen in the adsorbed water molecules and the lattice oxygen.     

Influence of ion bombardment on the profile of the depth distribution of impurity atoms in Si used for solar cells and diode structures

The chemical composition of the surfaces and surface layers of Si samples used in solar cells are studied using Auger electron spectroscopy (AES). It is shown that the low-energy implantation of Ba and O ions leads to the redistribution of impurity atoms in the surface layer and can prevent impurity atoms adsorbed onto the surface from penetrating inside the sample.     

Structural properties and diffusion processes of the Cu3Au (0 0 1) surface

The surface relaxation and surface energy of both the mixed AuCu and pure Cu terminated Cu₃Au (0 0 1) surfaces are simulated and calculated by using the modified analytical embedded-atom method. We find that the mixed AuCu termination is energetically preferred over the pure Cu termination thereby the mono-vacancy diffusion is also investigated in the topmost few layers of the mixed AuCu terminated Cu₃Au (0 0 1) surface. In the mixed AuCu terminated surface the relaxed Au atoms are raised above Cu atoms for 0.13 Å in the topmost layer. All the surface atoms displace outwards, this effect occurs in the first three layers and changes the first two inter-layer spacing. For mono-vacancy migration in the first layer, the migration energies of Au and Cu mono-vacancy via two-type in-plane displace: the nearest neighbor jump (NNJ) and the second nearest neighbor jump (2NNJ), are calculated and the results show that the NNJ requires a much lower energy than 2NNJ. For the evolution of the energy requirements for successive nearest neighbor jumps (SNNJ) along three different paths: circularity, zigzag and beeline, we find that the circularity path is preferred over the other two paths due to its minimum energy barriers and final energies. In the second layer, the NN jumps in intra- and inter-layer of the Cu mono-vacancy are investigated. The calculated energy barriers and final energies show that the vacancy prefer jump up to a proximate Cu site. This replacement between the Cu vacancy in the second layer and Cu atom in the first layer is remunerative for the Au atoms enrichment in the topmost layer.     

The oxidation of H2CO on a copper(110) surface

The oxidation of H₂C¹⁶O by adsorbed ¹⁸O was studied on an Cu(110) sample by temperature programmed reaction spectroscopy. Formaldehyde exchanged its oxygen with surface ¹⁸O upon adsorption to yield H₂C¹⁸O_(a) and ¹⁶O_(a). Formaldehyde was also oxidized by surface ¹⁶O and ¹⁸O atoms to H₂COO which subsequently released one of the hydrogen atoms to form HCOO. The evolution of H₂ from the Cu(110) surface was desorption limited, and the low pre-exponential factor for the recombination of the surface hydrogen atoms suggested stringent requirement on the trajectories of the colliding partners. The formate was very stable and dissociated at elevated temperatures to simultaneously yield H₂ and CO₂. The surface concentration of ¹⁸O exerted a pronounced affect on the activity of the oxidation of formaldehyde on Cu(110).     

SERS investigation of interfacial water at a silver electrode in acetonitrile solutions

Surface-enhanced Raman scattering from a silver electrode in solution of 0.1 M LiClO₄ in acetonitrile has been analyzed as a function of applied potential. Three ν(O-H) bands associated with the interfacial water and two ν(O-H) bands associated with the OH⁻ ion species were observed depending on the electrode potential. The band at 3487 cm⁻¹ is favored at relatively positive potentials and assigned to H₂O molecules interacting with the electrode surface via the oxygen atoms. Another band at 3586 cm⁻¹ appears in a wider potential region and is assigned to the H₂O molecules with one or both of the hydrogen atoms facing the electrode surface. Additionally, evidence for the possible surface ion pair, Li⁺OH⁻, which is closely associated with H₂O molecules and the quasi-crystalline form of LiOH are also presented in this paper.     

A study of the initial reaction of water vapor with Fe(001) surface

LEED and AES have been used to study the structural changes and kinetics of the initial interaction between Fe(001) and water vapor at temperatures from 298 to 473 K. A disordered c(2 × 2) structure was formed at all temperatures, and only 80% of the total number of sites were filled at saturation. The initial sticking coefficient was 0.56 ± 0.03, and the reaction rate increased with increasing temperature. A model was proposed that successfully accounted for these experimental observations. Irreversible chemisorption of water is proposed to take place via a precursor of physically adsorbed water molecules. The precursor, which is adsorbed on both bare surface and surface covered by chemisorbed species, is mobile and retains most of its degrees of rotational freedom. Water molecules in the precursor state can either desorb or dissociate, and the difference in activation energies for these reactions was found to be 5.7 ± 0.5 $\text{kcal}\text{mol}$. Only 80% of the available c(2 × 2) sites are filled and the surface layer is disordered because the chemisorbed species are immobile, and because each one blocks four nearest neighbor sites for further adsorption. The chemisorbed species occupy the fourfold symmetric sites either above the iron atoms or above the interstitial “holes” betweeh iron atoms.     

Analysis of hydrogen adsorption in the bulk and on the surface of magnesium nanoparticles

The stability of magnesium hydride (MgH _x ) nanoparticles (x = 0.5, …, 2) is investigated using ab initio calculations. It is shown that for a nanoparticle diameter of D ～ 5 nm, the internal pressure becomes lower than 3 kbar; for this reason, the structure of hydride nanoparticles coincides with the structure of this hydride in crystalline form. It is found that the phase of partly saturated MgH _x hydrides (x < 2) must decompose into the phase of pure hcp magnesium and the α phase of MgH₂. The frequencies of jumps of hydrogen atoms within the hcp phase of magnesium and in the α phase of MgH₂ are calculated; it is shown that slow diffusion of hydrogen in magnesium is due to the large height of potential barriers for motion of hydrogen within MgH₂. To attain high diffusion rates, the structures of Mg₅₃Sc and Mg₅₃Ti crystals and their hydrides are calculated. It is found that the frequency of jumps of H atoms in Mg₅₃ScH₁₀₈ near the Sc atoms does not noticeably change as compared to the frequency of jumps in the α phase of MgH₂, while the frequency of jumps in Mg₅₃TiH₁₀₈ near Ti atoms is higher by approximately a factor of 2.5 × 10⁶. This means that diffusion in manganese hydride with small admixtures of titanium atoms must be considerably eased. Chemical dissociation of hydrogen molecules on the (0001) surface of hcp magnesium, on the given surface with adjoined individual Ti atoms, and on the surface of a one-layer titanium cluster on the given surface of magnesium is investigated. It is found that dissociation of hydrogen at solitary titanium atoms, as well as on the surface of a Ti cluster, is facilitated to a considerable extent as compared to pure magnesium. This should also sharply increase the hydrogen adsorption rate in magnesium nanoparticles.     

Adsorption of water molecules on yttrium barium cuprate superconductors

Gravimetry and thermogravimetric analysis were used to study the adsorption of water molecules on the high temperature superconductor YBa₂Cu₃O₇ at room temperature. It was found that water adsorption subdivides into surface adsorption and bulk adsorption, which starts after the formation at the surface of a physically bound water layer no less than 65–100 Å thick. During bulk adsorption, H₂O molecules diffuse from this surface layer to the lattice, where they form four bound states with desorption temperatures of ～208, 330, 370, and 775°C and heats of formation of 38, 99, 72, and 68 kJ/mol, respectively, and mainly occupy interstitial sites of the intermediate layers. The presence of molecules in the lattice does not affect either the superconducting transition temperature or resistance to direct current; however, it results in an increase in the surface resistance. The resistance to direct current increases due to the formation of dielectric inclusions of other phases.