Chemisorption of CO on tungsten (100): Combined flash desorption and electron stimulated desorption study. II

The chemisorption of CO on W(100) at ~ 100K has been studied using a combination of flash desorption and electron stimulated desorption (ESD) techniques. This is an extension of a similar study made for CO adsorption on W(100) at temperatures in the range 200–300K. As in the 200–300 K CO layer, both α₁-CO and α₂-CO are formed in addition to more strongly bound CO species upon adsorption at ~ 100K; the α-CO states yield CO⁺ and O⁺ respectively upon ESD. At low CO coverages, the α₁ and α₂-CO states are postulated to convert to β-CO or other strongly bound CO species upon heating. At higher CO coverages, α₁-CO converts to α₂-CO upon thermal desorption or electron stimulated desorption. There is evidence for the presence of other weakly-bound states in the low temperature CO layer having low surface concentration at saturation. The ESD behavior of the CO layer coadsorbed with hydrogen on W(100) is reported, and it is found that H(ads) suppresses either the concentration or the ionic cross section for α₁ and α₂-CO states.     

X-ray induced electron stimulated desorption versus photon stimulated desorption: NH3 on Ni(110)

The X-ray induced desorption of H⁺ ions from NH₃ layers adsorbed at T = 90 K on Ni(110) has been compared to the corresponding total electron yield (TY) in the photon energy range 390 to 900 eV. The H⁺ yield exhibits a jump at the N K-edge and the Ni L-edge which inversely varies with the NH₃ layer thickness. The H⁺ Ni L-edge jump is closely correlated to the TY jump. Both vanish for the saturated NH₃ multilayer, indicating that the observed Ni L-edge jump in the H⁺ yield is exclusively due to X-ray induced electron stimulated desorption (XESD). At the N K-edge, the near edge absorption fine structure of the H⁺ yield and TY of the saturated NH₃ multilayer are distinctly different. This is interpreted as the H ⁺ yield being the superposition of direct photon stimulated ion desorption (PSID) and XESD. Based on the observed variation of the H⁺ yield near edge fine structure with varying NH₃ layer thickness, a deconvolution of the PSID and XESD contributions is used to derive the relative contribution of PSID versus XESD to be 40% versus 60%, respectively. The relevance of this result for future PSID-SEXAFS studies is discussed. For monolayer NH₃ on Ni(110) the polarization dependence of the N K-edge fine structure in the N(KVV) Auger yield indicates that the symmetry axis of NH₃, is perpendicular to the surface.     

Interaction of PH3 coadsorbed with H2, D2, O2 and H2O on Rh(100)

The coadsorption of PH₃ with H₂, D₂, O₂ and H₂O on Rh(100) has been studied using temperature programmed desorption (TPD), Auger electron spectroscopy (AES) and low energy electron diffraction (LEED). The adsorption and molecular desorption of PH₃ is not affected by preadsorbed H₂, D₂ and O₂. Preadsorbed PH₃ blocks H₂ desorption sites while postdosed PH₃ displaces H₂ (D₂₁) from the Rh(100). When D₂ and PH₃ are coadsorbed, no D appears in desorbed phosphine. Preadsorbed O₂ reduces the amount of H₂ desorption (from PH₃ decomposition) and increases the H₂ desorption temperature. There is also some reaction between O(a) and H(a) to form water. Preexposure to H₂O decreases the extent of PH₃ adsorption and of PH₃ decomposition.     

O2、 CO2和H2O在UN(001)表面化学吸附的密度泛函理论研究

采用广义梯度近似GGA,修正Perdew-Burke-Ernzerhof交换-关联泛函,以及周期性切片模型对O₂、CO₂和H₂O在UN(001)表面的化学吸附行为进行非自旋极化水平的密度泛函理论计算. 在四个对称性化学位置条件下,对化学吸附能与分子和UN(001)表面之间距离的关系曲线进行优化. 结果表明O₂、CO₂和H₂O分子的最稳定吸附位置分别为桥式平行、空心平行和桥式H     

Electron stimulated desorption of CO from Pd1/W(110)

The electron impact behavior of CO adsorbed on Pd₁/W(110) was investigated. The desorption products observed were neutral CO, CO⁺, and O⁺. After massive electron impact residual carbon, C/W = 0.15, but not oxygen was also found, suggesting that energetic neutral O, not detected in a mass analyzer must also have been formed. Formation of β-CO, i.e., dissociated CO with C and O on the surface was not seen. The total disappearance cross section varies only slightly with coverage, ranging from 9 × 10 ⁻¹⁸ cm² at low to 5 × 10⁻¹⁸ cm² at saturation (CO/W = 0.75). The cross section for CO⁺ formation varies from 4 × 10⁻²² cm² at satura to 2 × 10⁻²¹ cm² at low coverage. That for O⁺ formation is 1.4 × 10⁻²² cm² at saturation and 2 × 10⁻²¹ cm² Threshold energies are similar to those found previously [J.C. Lin and R. Gomer, Surf. Sci. 218 (1989) 406] for CO/W(110) and CO/Cu₁/W(110) which suggests similar mechanisms for product formation, with the exception of β-CO on clean W(110). It is argued that the absence or presence of β-CO in ESD hinges on its formation or absence in thermal desorption, since electron impact is likely to present the surface with vibrationally and rotationally activated CO in all cases; β-CO formation only occurs on surfaces which can dissociate such CO. It was also found that ESD of CO led to a work function increase of the remaining Pd₁/W(110) surface of 500 meV, which could be annealed out only at 900 K. This is attributed to surface roughness, caused by recoil momentum of energetic desorbing entities.     

Decomposition of CO2 on (100) W

The binding states and condensation kinetics of CO₂ and its decomposition products CO and O₂ on (100) W are examined by flash desorption mass spectrometry. Carbon dioxide desorbs almost entirely as CO and oxygen at all coverages. At saturation there are three major states of CO. These correspond to the high temperature states of CO alone although all peaks are shifted and amounts are altered slightly.     

Absolute coverage of C2H2 and C2H4 on Pt(111)

Quantitative XPS measurements have been performed in order to determine the absolute coverage of acetylene and ethylene adsorbed on Pt(111) showing a 2 × 2 LEED pattern. This LEED pattern has so far been attributed to a 2 × 2 superstructure with a coverage of 0.25. A quantitative evaluation of the C(1s) peak intensities for these adsorbed layers in comparison with adsorbed CO shows that the coverage is 0.5 instead of 0.25. Therefore the 2 × 2 LEED pattern should be assigned to a 2 × 1 superstructure in three domains rather than a 2 × 2 superstructure.     

Leed and thermal desorption studies of small molecules (H2, O2, CO,CO2, NO,C2H4, C2H2 AND C) chemisorbed on the rhodium (111) and (100) surfaces

The chemisorption of H₂, O₂, CO, CO₂, NO, C₂H₄, C₂H₂ and C has been studied on the clean Rh(111) and (100) surfaces. LEED, AES and thermal desorption were used to determine the surface structures, disordering and desorption temperatures, displacement and decomposition characteristics for each species. All of the molecules studied readily chemisorbed on both surfaces. A large variety of ordered structures was observed, especially on the (111) surface. The disordering temperatures of most ordered surface structures on the (111) surface were below 100°C. It was necessary to adsorb the gases at 25° C or below in order to obtain well-ordered surface structures. Chemisorbed oxygen was readily removed from the surface by H₂ or CO gas at crystal temperatures above 50°C. CO₂ appears to dissociate to CO upon adsorption on both rhodium surfaces as indicated by the identical ordering and desorption characteristics of these two molecules. C₂H₄ and C₂H₂ also had very similar ordering and desorption characteristics and it is likely that the adsorbed species formed by both molecules is the same. Decomposition of ethylene produced a sequence of ordered carbon surface structures on the (111) face as a result of a bulk-surface carbon equilibrium. The chemisorption properties of rhodium appear to be generally similar to those of iridium, nickel and palladium.     

Computer simulations of electron stimulated desorption patterns from oxygen on W(100) and (111) surfaces

Computer simulations of Electron-Stimulated-Desorption lon-Angular-Distribution patterns (ESDIAD) from oxygen covered W(100) and (111) surfaces were performed, using classcial dynamical formulas for the calculation of the O₊ ion trajectories. A model for the reconstruction of the O covered W(100) surface in the temperature range of 700–900 K is presented. The simulated ESD patterns have been brought into agreement with experimental results from literature by the proper choice: first of the repulsive atomic potentials acting on the ions, second of the rms amplitudes of the O atoms and third of the constants in the formula for Auger neutralization. The angular widths of the ESD spots were fitted by introducing bending vibrations of the chemisorbed O atoms and also by distributing the directions of the chemical bonds in limited angular areas. Assuming Franck-Condon type transitions and neglecting intermediate states, the final ion energies led to distances between the starting positions of the ions and the neighboring W atoms in the range of the known chemical bond lengths. The repulsive atomic potentials, obtained from Hartree-Fock-Slater self-consistent field calculations for W and O atoms in different electronic states and with different electronic charges, were compared with the potentials giving best agreement with the experimental ESDIAD results. In this way, qualitative conclusions concerning the electronic charge at the surfaces were derived.     

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.     

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.     

The coadsorption of CO and H2 on Fe(100)

The coadsorption of CO and hydrogen on an Fe(100) surface was studied by temperature programmed desorption and X-ray photoelectron spectroscopy. It was found that CO adsorption blocked the subsequent dissociative adsorption of H₂, although it did not seem to affect the hydrogen binding energy. Preadsorption of hydrogen was observed to reduce the binding energy of CO subsequently adsorbed and to inhibit the dissociation of CO. A new surface species was identified in a coadsorbed layer of CO and hydrogen. This species was evidenced by the formation of a desorption peak for H₂ at 475 K when CO was adsorbed subsequent to H₂ adsorption.     

Hydrogen on W (100): Electron stimulated desorption and a structural model

Prompted by the peculiar shape of the curve of election-induced H⁺ current versus coverage for hydrogen on W(100) which has been observed before, we have restudied this system by correlated ESD, thermal desorption, and LEED measurements. The maxima in ESD signal and intensity of the half-order LEED spots, and the appearance of a second desorption peak are roughly correlated at $\text{1}\text{4}$ coverage. Using this observation and the exact shape of the ESD curve, a structural model is derived in which two different, but uniform states (i and f) exist, the first, i, being exclusively occupied up to $\text{1}\text{4}$ monolayer, and the second, f, at saturation. A gradual conversion from i to f takes place at $\text{1}\text{4}\text{< θ < 1}$ which is caused by the interaction between adsorbed H atoms. From this model a differential equation for the occupation numbers of i and f states, respectively, is derived and solved numerically; it yields good agreement with the experimental ESD curve. Discussing the possible physical realization of the two states, it can be made probable that they must exist on two different sites and have fourfold (i) and twofold (f) symmetry, so that the conversion is accompanied by a shift of the binding site of the adatom.     

Photon and electron stimulated desorption of adsorbates from W {100}

We have performed photon and electron stimulated desorption (PSD and ESD) studies of F⁺, Cl⁺ and O⁺ ions from a W {100} surface and have measured the kinetic energies for a small range of emission angles of these ions as well as the effect of different electron and photon excitation energies. We find that the PSD and ESD processes show essentially the same threshold energies and produce the same ion energy and angle distribution, and so evidently involve the same mechanism. For the case of O⁺ we also find clear evidence that substrate core-level excitation initiates the desorption process as proposed by Knotek and Feibelman for adsorbates bonded to surface atoms with a maximal valency configuration. The substrate levels are not seen to play a role in the F⁺ and Cl⁺ desorption, indicating a very different type of bonding for these species on the W 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.     

LEED and thermal desorption studies of small molecules (H2, O2, CO,CO2, NO,C2H4, C2H2 and C) chemisorbed on the stepped rhodium (755) and (331) surfaces

The chemisorption of H₂, O₂, CO, CO₂, NO, C₂H₂, C₂H₄ and C has been studied on the clean stepped Rh(755) and (331) surfaces. Low energy electron diffraction (LEED), Auger electron spectroscopy (AES) and thermal desorption spectroscopy (TDS) were used to determine the size and orientation of the unit cells, desorption temperatures and decomposition characteristics for each adsorbate. All of the molecules studied readily chemisorbed on both stepped surfaces and several ordered surface structures were observed. The LEED patterns seen on the (755) surface were due to the formation of surface structures on the (111) terraces, while on the (331) surface the step periodicity played an important role in the determination of the unit cells of the observed structures. When heated in O₂ or C₂H₄ the (331) surface was more stable than the (755) surface which readily formed (111) and (100) facets. In the CO and CO₂ TDS spectra a peak due to dissociated CO was observed on both surfaces. NO adsorption was dissociative at low exposures and associative at high exposures. C₂H₄ and C₂H₂ had similar adsorption and desorption properties and it is likely that the same adsorbed species was formed by both molecules.     

Desorption of H2 from W(110) and Fe covered W(110) surfaces

The kinetics of H₂ desorption from H/W(110) and H/Fe₁/W(110) were studied by measuring work function changes Δø vs time at a number of temperatures. Combination with previously determined Δø vs coverage data and differentiation at various fixed coverages gave rate vs T data from which activation energies of desorption could be obtained. E vs coverage results agree well with previously determine ΔH_des results. In the case of H/Fe₁/W(110) this includes a rise from 20 to 30 kcal mol⁻¹ of H₂ at H/Fe = H/W > 0.3. Plots of rate −dθ/dt vs θ (θ being coverage in units of H/W) vary much more steeply than θ² at most coverages for both systems. The θ dependence can be explained almost quantitatively in terms of the variations of ΔH_des and surface entropy S_s with coverage, by assuming that rates of desorption are equal to the equilibrium rates of adsorption. The latter can be formulated thermodynamically, except for a sticking coefficient, s. Values for s(θ, T) can also be obtained and show relatively little temperature dependence.     

Li掺杂对MgH2(001)表面H2分子扩散释放影响的第一性原理研究

本文利用基于密度泛函理论的第一性原理分别研究了MgH₂(001)表面H原子扩散形成H₂分子释放出去的可能路径及金属Li原子掺杂对其影响. 研究结果表明: 干净MgH₂(001)表面第一层释放H原子形成H₂分子有两种可能路径, 其释放能垒分别为2.29和2.50 eV; 当将Li原子替代Mg原子时, 两种H原子扩散释放路径的能垒分别降到了0.31和0.22 eV, 由此表明Li原子掺杂使MgH₂(001)表面H原子扩散形成H₂释放更加容易.