Structure of CO adsorbed on Ni (100)

The c(2 × 2) configuration of CO chemisorbed on Ni(100) has been examined by the dynamical LEED method of surface structure analysis. Experimental LEED intensity spectra of the (00), ($\text{1}\text{2}\text{1}\text{2}$) (10) and (11) LEED beams measured at 175 K are compared with the corresponding calculated spectra for two different CO potential constructions and a number of trial structures. The best agreement was found for a structure where the CO molecules sit directly above the Ni atoms with vertical spacings between the Ni and C and the C and O layers of 1.80 ± 0.10 A and 0.95 ± 0.10 Å respectively. It is proposed that the CO molecule is tipped over at an angle of 34° ± 10° with respect to the surface normal so that the actual carbon-oxygen bond length is close to the figure 1.15 Å found in Ni(CO)₄.     

Low-energy electron diffraction,Auger electron spectroscopy,and thermal desorption studies of chemisorbed CO and O2 on the (111) and stepped [6(111) × (100)] iridium surfaces

The adsorption of CO, O₂, and H₂O was studied on both the (111) and [6(111) × (100)] crystal faces of iridium. The techniques used were LEED, AES, and thermal desorption. Marked differences were found in surface structures and heats of adsorption on these crystal faces. Oxygen is adsorbed in a single bonding state on the (111) face. On the stepped iridium surface an additional bonding state with a higher heat of adsorption was detected which can be attributed to oxygen adsorbed at steps. On both (111) and stepped iridium crystal faces the adsorption of oxygen at room temperature produced a (2 × 1) surface structure. Two surface structures were found for CO adsorbed on Ir(111); a (√3 × √3)R30° at an exposure of 1.5–2.5 L and a (2√3 × 2√3)R30° at higher coverage. No indication for ordering of adsorbed CO was found on the Ir(S)-[6(111) × (100)] surface. No significant differences in thermal desorption spectra of CO were found on these two faces. H₂O is not adsorbed at 300 K on either iridium crystal face. The reaction of CO with O₂ was studied on Ir(111) and the results are discussed. The influence of steps on the adsorption behaviour of CO and O₂ on iridium and the correlation with the results found previously on the same platinum crystal faces are discussed.     

Molecular orbital study of the interaction of carbon monoxide and carbon dioxide with copper (100)

A molecular orbital study is made of the structures and energy levels of CO and CO₂ on Cu(100). The importance of self-consistency is discussed. CO is found to occupy fourfold indentations, in agreement with the semiempirical results of Doyden and Ertl. The C-surface distance is 1.0 Å and the CO bond stretches less than 0.1 Å. Large models of the surface show convergence of the electronic structure with four CO molecules on a twelve Cu atom cluster model of the surface. At coverages up to c(2 × 2) half monolayer, calculated energy levels match Demuth and Eastman's phase I photoemission spectrum. Phase II, as observed by them, has no analog in the calculations. No evidence is found for CO deviating from perpendicular to the surface when tightly bound. CO₂ is found to adsorb more weakly to the surface. This molecule rests in a μ bridging position, bonded through mixing of Cu d with CO₂ π¹ orbitals. It bends, with an angle of 120°, which is significantly similar to 122° for the ¹B₂ excited state of free CO₂, which has an electron promoted to the π¹ orbital. On the basis of this molecular orbital study, extrapolations to Ni and Zn surfaces and OCS, CS₂, CSe₂ and CTe₂ are made.     

Chemisorption studies on cobalt single crystal surfaces: I. Carbon monoxide on Co(0001)

The chemisorption of CO on Co(0001) and on a polycrystalline specimen has been studied by LEED, Auger spectroscopy, and thermal desorption measurements. Annealing of the polycrystal was found to result in a surface dominated by crystallites of (0001) orientation in the surface plane, along with a few (101̄2) oriented crystallites. CO adsorbs on the clean surface at 300 K with an initial sticking probability of 0.9 and the system follows precursor state kinetics. The saturation coverage under UHV conditions corresponds to a well-ordered (√3 × √3)R30° structure; with P_CO>5 × 10^-9 a uniform compression of the adlayer takes place and a (√7 × √7)R19.2° structure begins to form. Models are proposed for these two ordered phases which are in agreement with the observed relative coverage data and the appearance of the corresponding desorption spectra. The desorption enthalpy of CO at low coverages is 103 ± 8 kJmol^-1, and a fairly sharp fall in this enthalpy occurs for coverages $\text{>}\text{1}\text{3}$. In many respects, the system's behaviour closely resembles that of Ni(111)-CO. Oxygen contamination leads to the appearance of a strongly adsorbed CO state with a desorption enthalpy of ~170 kJmol^-1. This is reminiscent of a strongly adsorbed non-dissociated state of CO on Ru(101̄1) which occurs under similar conditions.     

Coadsorption of oxygen and carbon monoxide on tungsten: Desorption spectra,electron stimulated desorption and field emission microscopy

CO/W desorption spectra are characterized by an α state and multiple β states; using electron stimulated desorption (ESD) the α state was shown to comprise two sub-states, α₁ and α₂. In this paper the consecutive interactions of O₂ and CO on W are investigated using ESD, flash desorption and field emission microscopy (FEM).Desorption spectra show that the α-CO state is displaced by O₂, in two stages. The ESD probe provides an identification of the first stage with the removal of the α₁-CO state, and energy analysis of ESD ions reveals a large energy shift (～ ? 1.5 eV) during O₂ coadsorption which can be attributed to an incresae in the α₁-CO WC bond length of ～ 0.15 Å. During this O₂-induced displacement, the two β peaks converge into a single peak at the β₁ position; this is ascribed to adatom interactions in the mixed O and C adlayer. Isotope exchange experiments with ²⁸CO and ³⁶O₂ reveal (i) no exchange in the α-CO states, and (ii) complete exchange in the β-CO states, which is consistent with dissociative adsorption in the latter. The amount of coadsorbed O₂ is estimated from these results, and from FEM data: a full monolayer of O adatoms can be coadsorbed on CO-saturated W, but CO pre-adsorption inhibits the formation of W oxides. The β₁-O₂ (ESD active) state also forms on the CO-covered surface: this state is identical in population, ESD cross section and ion energy distribution to β₁-O₂ on clean W, and retains its identity in the mixed layer (it does not undergo isotopic exchange). CO₂ desorption spectra from the mixed layer were also characterised, complete isotopic scrambling being observed.Pre-exposure of tungsten to O₂ inhibits CO adsorption: a monolayer of O₂ is sufficient to prevent CO adsorption, and at low O₂ coverages, every O₂ molecule preadsorbed prevents one CO molecule from adsorbing. Isotopic exchange is again complete in the β states, and a lateral interaction model for desorption kinetics, based on dissociative adsorption in the β-CO state, quantitatively describes the CO desorption spectra.     

X-Ray Reflectometry of DMPS Monolayers on a Water Substrate

The molecular structure of dimyristoyl phosphatidylserine (DMPS) monolayers on a water substrate in different phase states has been investigated by X-ray reflectometry with a photon energy of ~8 keV. According to the experimental data, the transition from a two-dimensional expanded liquid state to a solid gel state (liquid crystal) accompanied by the ordering of the hydrocarbon tails C₁₄H₂₇ of the DMPS molecule occurs in the monolayer as the surface pressure rises. The monolayer thickness is 20 ± 3 and 28 ± 2 Å in the liquid and solid phases, respectively, with the deflection angle of the molecular tail axis from the normal to the surface in the gel phase being 26° ± 8°. At least a twofold decrease in the degree of hydration of the polar lipid groups also occurs under two-dimensional monolayer compression. The reflectometry data have been analyzed using two approaches: under the assumption about the presence of two layers with different electron densities in the monolayer and without any assumptions about the transverse surface structure. Both approaches demonstrate satisfactory agreement between themselves in describing the experimental results.     

The adsorption of carbon monoxide on Cu(110)-Ni surfaces prepared by dissociation of nickel carbonyl

Cu(110)-Ni surface alloys were prepared by dissociation of nickel carbonyl on clean Cu(110). The adsorption of CO is reversible in the temperature region of 22–200°C and the pressure range of 5 × 10^?8-0.7 Torr, as monitored with ellipsometry and AES. The amount of adsorbed CO depends on the amount of preadsorbed oxygen but not on the amount of carbon present at the surface. The isosteric heat of adsorption decreases from 31 ± 3kcal/mole to 18 ± 2 kcal/mole with increasing CO coverage (up to θ = 0.14θ_max) but is constant for higher coverages (up to θ = 0.4θ _max).     

CO chemisorption on PtCu surfaces I. CO on (1 × 3) Pt0.98Cu0.02(110)

Thermal desorption and photoemission spectroscopy (PES) have been used to investigate the chemisorption of CO on an annealed Pt_0.98Cu_0.02(110) surface. The clean surface shows 9.1 ± 2.6% Cu within the top 4 Å, and is (1 × 3) reconstructed. Thermal desorption of CO has revealed the existence of various adsorption states with these respective heats of adsorption: (α) 35.2 to 37.8 kcal/mol and (β) 24.5 to 26.3 kcal/mol on Pt sites, (γ) 16.0 to 17.2 kcal/mol on PtCu “mixed” sited, and (δ) 12.9 to 13.9 kcal/mol on Cu sites. PES observation of Cu 3d-derived states (using hv = 150 eV) and the $\text{Cu 2p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ core levels (using Mg Kα radiation) shows that the electronic structure of the Cu constituent is changed only when CO adsorbs on the Pt-Cu “mixed” sites or the Cu sites. Furthermore, the CO states associated with Pt sites reflect the structural difference between the (1 × 3) alloy surface and the (1 × 2) pure Pt(110) surface: α-CO on the alloy surface desorbs at a temperature 17 to 21 K. higher than the maximum desorption temperature of CO from pure Pt(110), and the ratio of β-CO to α-CO desorption from the alloy surface is larger than the ratio of low temperature to high temperature peaks in the desorption of CO from pure Pt(110).     

Intensity dependence of multiphoton dissociation in formaldehyde

A new intensity-dependent measurement of multiple-photon dissociation (MPD) in H₂CO, HDCO, and D₂CO gases by the use of an intense pulsed CO₂TEA laser is reported. In this measurement the energy and duration of the laser pulses are kept constant, and the intensity is varied by irradiating the sample using concave mirrors of different focal lengths. A model calculation is used to analyze and fit the present and previous experimental MPD data of HDCO and D₂CO. In this model it is assumed that dissociation is obtained by a repeated mechanism in which coherent multiphoton excitation (CME) of the molecule to high vibration-rotation states |v, J〉 is followed by intramolecular transfer of the excitation energy (ITEE) to the other modes of the molecule. In the calculations the CME is described in the framework of the density matrix formalism with relaxations, and is used to calculate absorption from the ground state as well as absorption from excited states reached by the energy redistribution in the molecule. The ITEE process is assumed to be intensity independent and to cause a random energy distribution in each transferring process. It is found that the experimental results are consistent with the absorption of 14±4 and 17±5 photons per molecule for HDCO and D₂CO, respectively, and this is sufficient to cause their dissociation.     

Adsorption and reaction of CO2 and CO2/O CO-adsorption on Ni(110): Angle resolved photoemission (ARUPS) and electron energy loss (HREELS) studies

Molecular adsorption is observed on a Ni(110) surface at 80 K. The relative binding energies of the valence ion states as determined by ARUPS are consistent with those in the gas as well as in the condensed phase, and indicate that the electronic structure of the adsorbed molecule is only slightly distorted upon adsorption at this temperature. The adsorbate spectra show E versus k_∥ dispersions indicating some long-range order in the adsorbate. The variations in relative ionisation probabilities of the ion states as a function of electron emission angle suggest that the molecular axis is oriented parallel to the surface within ± 20°. Upon heating the adsorbate to above 100 K. (i.e. 140 K) the spectrum changes. A new species causing an increase in work function by 1 eV can be identified. Comparison with calculations suggests that it is an anionic bent CO; molecule. Electron energy loss studies on this intermediate species support the proposed bent CO₂ geometry and favour a coordination site with C_2v symmetry. The bent CO₂ moiety is stable up to 230 K. Further heating to room temperature leads to dissociation of the bent CO₂ molecule into adsorbed CO and O. The CO molecule is oriented with its axis perpendicular to the surface. The bent CO₂ species appears to be a precursor to dissociation. Results on CO₂ adsorption on an oxygen precovered surface show that CO₂ interacts with oxygen at 85 K. Upon heating the co-adsorbate to near room temperature a reaction product is formed the nature of which cannot yet be clearly identified.     

XPS study of WC formation process

The surface composition and chemical bonding state of WO₃ carburized in CO at 700°C have been investigated with X-ray photoelectron spectroscopy, in order to clarify the mechanism of WC formation. The experimental results show that the carburization process is based on a direct reaction of WO_x (x≦3) with free carbon which accumulates on the WO_x surface by the disproportionation of CO. A model for the WC formation process is also presented.     

A first principles study of the adsorption and dissociation of CO<Subscript>2</Subscript> on the δ-Pu (111) surface

A complete understanding of the nature of the 5f electrons has been and continues to be a major scientific problem in condensed matter physics. Bulk and surface electronic structure studies of the actinides as also atomic and molecular adsorptions on the actinide surfaces provide a path towards this understanding. In this work, ab initio calculations within the framework of density functional theory have been used to study the adsorption of molecular CO₂ and the corresponding partially dissociated (CO + O) and completely dissociated (C + O + O) products on the δ-Pu (111) surface. The completely dissociated C + O + O configurations exhibit the strongest binding with the surface (7.92 eV), followed by partially dissociated products CO + O (5.08 eV), with molecular CO₂ adsorption having the lowest binding energies (2.35 eV). For all initial vertically upright orientations, the CO₂ molecule physisorbs or do not bind to the surface and the geometry and orientation do not change. For all initial flat lying orientations chemisorption occurs, with the final state corresponding to a bent CO₂ molecule with bond angles of 117°–130° and the elongation of the CO bond. For CO + O co-adsorption, the stable configurations corresponded to CO dipole moment orientations of 100°–172° with respect to the surface normal and the elongation of the CO bond. The most stable chemisorption cases correspond to anomalously large rumpling of the top Pu layer. The interactions of the CO₂ and CO with the Pu surface have been analyzed using the energy density of states and difference charge density distributions. The nature and the behavior of the 5f electrons have also been discussed in detail in the context of this study.     

Auger spectroscopic study of the surface composition of Pt/Sn alloys in ultrahigh vacuum and in the presence of oxygen and hydrogen

The surface composition of two Pt/Sn alloys, viz. PtSn and Pt₃Sn, has been followed by means of AES, as a function of annealing in ultrahigh vacuum, oxygen chemisorption and reduction with hydrogen.The results, which were quantitatively interpreted with the aid of a novel calibration technique, reveal the following features: - The surface of PtSn and Pt₃Sn becomes enriched with tin by annealing in vacuum. Ultimate values of 68±5 at% Sn for PtSn and 41±5 at% Sn for Pt₃Sn were attained after annealing at 500°C. - The adsorption of oxygen on the annealed surface of PtSn and Pt₃Sn causes a further enrichment with tin, while severe oxidation of PtSn at 500°C leads to complete disappearance of Pt from the surface. - Oxygen is more strongly and differently bound on a surface containing about 40 at% Sn than on a surface containing about 70 at% Sn. Activated adsorption of oxygen takes place only on the latter. The results suggest the formation of SnO₂ surface complexes on the exposed surface of Pt₃Sn. - Reduction of the alloys at 500°C carries the excess of tin into the bulk and reduces its surface concentration to 35±5 at% for Pt₃Sn and 64±5 at% for PtSn, which is an enrichment of the surface with platinum relative to the annealed state.     

用低能电子衍射谱计算过渡金属吸附CO的表面结构

本文用低能电子衍射谱研究了CO分子吸附在过渡金属上的表面结构。     

CO2在Pd表面吸附的热力学

 用密度泛函方法和相对论有效原子实势,分别对PdCO₂,PdCO和PdH的基态几何构型进行优化, 得到PdCO₂分子基态为Cs构型, Pd与CO2分子在同一平面, 键长PdC为0.203 0 nm, CO为0.118 3 nm, CO′为0.121 0 nm, 键角∠OCO′为154.215°,电子状态为1A′; PdCO分子基态电子状态为1+, 键长PdC为0.183 4 nm, CO为0.114 0 nm, 键角∠PdCO为180°; PdH分子基态为2∑, 键长PdH为0.152 6 nm。根据电子-振动近似理论计算了不同温度下金属Pd 与CO₂,CO及H2分子反应的生成热力学函数, 导出了反应平衡压力随温度的变化关系。分析认为杂质CO₂气体引起Pd合金膜中毒可能是由于CO₂分子吸附在Pd膜表面,形成Pd的CO₂化合物后,再自发分解为PdO和CO,而使Pd表面出现O和CO中毒所致。     

The effect of microtacticity on the glass temperature of poly[α-methyl styrene]

The effect of micrestructure on the glass temperature Tg of poly (α-methyl styrene) has been investigated. It has been observed that T_g increases as the syndiotacticity of the molecule increases-thus T_g = 446 ± 2°K for polymer with 67% syndiotactic placements, while a value of T_g = 453 ± 2°K is found for a sample with 95% syndiotactic placements. Coefficients of expansion for the liquid and glassy states have been calculated and from these a chain stiffness parameter δε/k has been estimated using the Gibbs-DiMarzio theory. The result indicates that the flex energy of the α-methyl styrene chain is 20% larger than for the polystyrene chain.     

Adsorption of carbon monoxide,oxygen, hydrogen,nitrogen, ethylene and benzene on an iridium (110) surface; Correlation with other iridium crystal faces

The interaction of CO, O₂, H₂, N₂, C₂H₄ and C₆H₆ with an Ir(110) surface has been studied using LEED, Auger electron spectroscopy and flash desorption mass spectroscopy. Adsorption of oxygen at 30°C produces a (1× 2) structure, while a c(2 × 2) structure is formed at 400°C. Two peaks have been detected in the thermal desorption spectrum of oxygen following adsorption at 30°C. The heat of adsorption of hydrogen is slightly higher on Ir(110) than on Ir(111). Adsorption of carbon monoxide at 30°C produces a (2 × 1) surface structure. The main CO desorption peak is found around 230, while two other desorption peaks are observed around 340 and 160°C. At exposures between 250 and 500°C carbon monoxide adsorption yields a c(2 × 2) structure and a desorption peak around 600°C. Carbon monoxide is adsorbed on an Ir(110) surface partly covered with oxygen or carbon in a new binding state with a significantly higher desorption temperature than on the clean surface. Adsorption of nitrogen could not be detected on either clean or on carbon covered Ir(110) surfaces. The hydrocarbon molecules do not form ordered surface structures on Ir(110). The thermal desorption spectra obtained after adsorption of C₆H₆ or C₂H₄ are similar to those reported previously for Ir(111) consisting mostly of hydrogen. Heating the (110) surface above 700°C in the presence of C₆H₆ or C₂H₄ results in the formation of an ordered carbonaceous overlayer with (1 × 1) structure. The results are compared with those obtained previously on the Ir(111) and Ir(755) or stepped [6(111) × (100)] surfaces. The CO adsorption results are discussed in relation to data on similar surfaces of other Group VIII metals.     

On the Auger inverse sensitivity factors of In and Sb in InSb

The Auger inverse sensitivity factors α_i for In and Sb on a (111) In surface of an InSb crystal mounted on a 30° sample holder were determined as 0.56 ± 0.04 and 0.67 ± 0.05, respectively, by Auger Electron Spectroscopy (AES). These values were referenced to the clean Si 92 eV peak and differ significantly from those obtained for In and Sb when in their elemental form. Angular dependent variations in the α_i values were observed upon rotation of the sample about its normal.     

Effects of adsorbates on electron spin polarization in low energy electron diffraction from tungsten (001): II. Ordered CO overlayer

Electron spin polarization and intensity profiles have been measured in low electron diffraction (LEED) for the (00) beam at θ = 13° and ø = 0° from a W(001) surface exposed to CO and annealed to obtain an ordered c(2 × 2) CO overlayer. The annealed surface with additional CO adsorbed was also studied. The polarization was found to be sensitive to the surface condition and the very distinct P?V profile corresponding to the c(2 × 2) overlayer is believed to be a very sensitive indicator of CO in the β₃ phase. The properties of the annealed surface exposed to further CO suggest the use of this surface as a low energy electron spin polarization analyzer.     

Verzweigungsverhältnisse und Konversionskoeffizienten von angeregten Zuständen des208Tl

The branching ratios of theγ rays of the second and fourth excited states of²⁰⁸Tl have been investigated by coincidence measurements between the α rays of²¹²Bi and subsequent 40keVγ ray. The detectors employed were a silicon surface barrier counter for α particles, and a 1.5 in ×2 mm NaJ (Tl) crystal forγ rays. It has been found that (75.6±3.7)% of all transitions of the 328 keV state and (94±7)% of all transitions of the (492 keV+473 keV) states populate the first excited state of²⁰⁸Tl. The 40 keV state is excited to (3.4±0.3)% by transitions of higher excited states relative to the direct excitation by α particles. The number of α particles with energyE _α = 6.047 MeV and the number of subsequent 40keVγ rays resulted in a conversion coefficient α(40keV)=22.55± 0.46. Similarly coincidence measurements between Tl-x rays and α particles have been used to determine theK- conversion coefficients α_K(328 keV)=0.31±0.03 and α_K(492 keV+ 473keV)=0.100±0.015. The experimental results are in good agreement with the theoretical values ofSliv.