Adsorption and dissociation of CO on Fe(1 1 0) from first principles

We employ spin-polarized periodic density functional theory (DFT) to characterize CO adsorption and dissociation on the Fe(1 1 0) surface. We investigate the site preference for CO on Fe(1 1 0) at θ_CO = 0.25 and 0.5 monolayer (ML), for different functional forms of the generalized gradient approximation (GGA) to electron exchange and correlation within DFT. At 0.25 ML, we predict the existence of a new ordered structure comparable in stability to one proposed previously. At 0.5 ML, we confirm the preference of a distorted on-top adsorption configuration suggested by experiment. The calculated heats of adsorption, CO stretching frequencies, and work function changes agree well with experiment. When dissociating from the on-top site, we predict that CO first moves off the on-top site and then goes through a lying-down transition state with a barrier of 1.52 eV. Diffusion of CO on Fe(1 1 0) from the on-top site to the long-bridge site is predicted to have a very small barrier of 0.1 eV. Dissociation of CO from the long-bridge site goes through the same transition state as from the on-top site, but the former has a slightly lower barrier. After dissociation, O atoms remain on the surface while C atoms are embedded into Fe(1 1 0), indicating C atoms may readily diffuse into Fe(1 1 0).     

Sum frequency generation and density functional studies of CO-H interaction and hydrogen bulk dissolution on Pd(1 1 1)

CO-H interaction and H bulk dissolution on Pd(1 1 1) were studied by sum frequency generation (SFG) vibrational spectroscopy and density functional theory (DFT). The theoretical findings are particularly important to rationalize the experimentally observed mutual site blocking of CO and H and the effect of H dissolution on coadsorbate structures. Dissociative hydrogen adsorption on CO-precovered Pd(1 1 1) is impeded due to an activation barrier of ∼2.5 eV for a CO coverage of 0.75 ML, an effect which is maintained down to 0.33 ML CO. Preadsorbed hydrogen prevented CO adsorption at 100 K, while hydrogen was replaced from the surface by CO above 125 K. The temperature-dependent site blocking of hydrogen originates from the onset of hydrogen diffusion into the Pd bulk around 125 K, as shown by SFG and theoretical calculations using various approaches. When Pd(1 1 1) was exposed to 1:1 CO/H₂ mixtures at 100 K, on-top CO was absent in the SFG spectra although hydrogen occupies only threefold hollow sites on Pd(1 1 1). DFT attributes the absence of on-top CO to H atoms diffusing between hollow sites via bridge sites, thereby destabilizing neighboring on-top CO molecules. According to the calculations, the stretching frequency of bridge-bonded CO with a neighboring bridge-bonded hydrogen atom is redshifted by 16 cm⁻¹ when compared to bridging CO on the clean surface. Implications of the observed effects on hydrogenation reactions are discussed and compared to the C₂H₄-H coadsorption system.     

CO在Pu(100)表面吸附的研究

采用密度泛函理论(DFT)研究了CO分子在Pu (100)面上的吸附. 计算结果表明：CO在Pu (100)表面的C端吸附比O端吸附更为有利，属于强化学吸附. CO吸附态的稳定性为穴位倾斜>穴位垂直>桥位>顶位. CO分子与表面Pu原子的相互作用主要源于CO分子的杂化轨道和Pu原子的杂化轨道的贡献. 穴位倾斜吸附的CO分子的离解能垒较小(0.280eV)，表明在较低温度下，CO分子在Pu (100)表面会发生离解吸附，离解的C，O原子将占据能量最低的穴位.     

CO在Pu(100)表面吸附的研究

采用密度泛函理论(DFT)研究了CO分子在Pu (100)面上的吸附. 计算结果表明：CO在Pu (100)表面的C端吸附比O端吸附更为有利,属于强化学吸附. CO吸附态的稳定性为穴位倾斜>穴位垂直>桥位>顶位. CO分子与表面Pu原子的相互作用主要源于CO分子的杂化轨道和Pu原子的杂化轨道的贡献. 穴位倾斜吸附的CO分子的离解能垒较小(0.280eV),表明在较低温度下,CO分子在Pu (100)表面会发生离解吸附,离解的C,O原子将占据能量最低的穴位. 关键词： 密度泛函理论 Pu (100) CO 分子和离解吸附     

Benzene adsorption on the Rh(111) metal surface: A theoretical study

The chemisorption of benzene on the Rh(111) surface is studied in the general framework of the extended Hückel theory, with optimized Rh parameters. MO arguments are used to discuss the main features of the electronic interaction of the aromatic system with the surface. Binding energy curves for adsorption on the most likely surface sites are computed, and the effect of the CH bond back-bending and of tilting of the benzene plane are examined. The most favorable chemisorption geometry is found when the C-atom ring is parallel to the surface and the center of the ring is above a threefold hollow site, but H atoms are farther away from the surface than C atoms. The optimum CRh distance compares well with those found in metal complex molecules. The on-top site is unfavorable for benzene chemisorption. The results of tight-binding calculations on infinite slabs agree with, and support, those of simple cluster calculations. A slight “Kekulé distortion” and a small activation barrier to chemisorption are predicted.     

The co-adsorption of oxygen and hydrogen on Rh(111)

The co-adsorption of oxygen and hydrogen on Rh(111) at temperatures below 140 K has been studied by thermal desorption mass spectrometry, Auger electron spectroscopy, and lowenergy electron diffraction. The co-adsorption phenomena observed were dependent upon the sequence of adsorption in preparing the co-adsorbed overlayer. It has been found that oxygen extensively blocks sites for subsequent hydrogen adsorption and that the interaction splits the hydrogen thermal desorption into two states. The capacity of the oxygenated Rh(111) surface for hydrogen adsorption is very sensitive to the structure of the oxygen overlayer, with a disordered oxygen layer exhibiting the lowest capacity for hydrogen chemisorption. Studies with hydrogen pre-adsorption indicate that a hydrogen layer suppresses completely the formation of ordered oxygen superstructures as well as O₂ desorption above 800 K. This occurs with only a 20% reduction in total oxygen coverage as measured by Auger spectroscopy.     

CO adsorption on Cu(1 1 1) and Cu(0 0 1) surfaces: Improving site preference in DFT calculations

CO adsorption on Cu(1 1 1) and Cu(0 0 1) surfaces has been studied within ab initio density functional theory (DFT). The structural, vibrational and thermodynamic properties of the adsorbate–substrate complex have been calculated. Calculations within the generalized gradient approximation (GGA) predict adsorption in the threefold hollow on Cu(1 1 1) and in the bridge-site on Cu(0 0 1), instead of on-top as found experimentally. It is demonstrated that the correct site preference is achieved if the underestimation of the HOMO–LUMO gap of CO characteristic for DFT is corrected by applying a molecular DFT + U approach. The DFT + U approach also produces good agreement with the experimentally measured adsorption energies, while introducing only small changes in the calculated geometrical and vibrational properties further improving agreement with experiment which is fair already at the GGA level.     

First-principles study of Ar adsorptions on the （111） surfaces of Pd, Pt, Cu, and Rh

In the present paper we give a detailed report on the results of our first-principles investigations of Ar adsorptions at the four high symmetry sites on M （111） （M =Pd, Pt, Cu, and Rh） surfaces. Our studies indicate that the most stable adsorption sites of Ar on Pd （111） and Pt （111） surfaces are found to be the fcc-hollow sites. However, for Ar adsorptions on Cu （111） and Rh （111） surfaces, the most favorable site is the on-top site. The density of states （DOS） is analyzed for Ar adsorption on M （111） surfaces, and it is concluded that the adsorption behavior is dominated by the interaction between 3s, 3p orbits of Ar atoms and the d orbit of the base metal atoms.     

Relaxation of the (1 1 1) surface of δ-Pu and effects on atomic adsorption: An ab initio study

The computational formalism of the full-potential all-electron linearized augmented plane wave plus local orbitals (FP-LAPW+lo) method has been employed to study the relaxation of the δ-Pu(1 1 1) surface and the consequent effects for atomic adsorption of C, N, and O atoms on this surface. The underlying theoretical principle is the generalized gradient approximation to density functional theory (GGA-DFT) and the surface was modeled by a five-layer slab with a (2×2) surface unit cell. Upon relaxation of the slab, the interlayer separation between the surface and the subsurface layers expanded by 7.1% with respect to the bulk interlayer separation, while the separation between the subsurface and central layers expanded by 0.4%. To study adsorption on the surface, the adatoms were allowed to approach the surface at four high symmetry adsorption sites, namely, the top, bridge, hollow FCC, and hollow HCP sites, the adlayer structure corresponding to a coverage of 0.25 of a monolayer in all cases. The hollow FCC adsorption site was found to be the most stable site for C and N with chemisorption energies of 6.420 and 6.549 eV, respectively, while the hollow HCP adsorption site was found to be the most stable site for O with a chemisorption energy of 7.858 eV. The respective distances of the C, N, and O adatoms from the surface were found to be 1.22, 1.09, and 1.22 Å. The work function and net magnetic moments, respectively, increased and decreased in all cases upon chemisorption compared with the bare δ-Pu(1 1 1) surface. The electronic structure of the interactions between the adsorbates and the substrate is discussed in detail.     

The coadsorption of potassium and co on the pt(111) crystal surface: A TDS,HREELS and UPS study

The interaction of CO with a potassium covered Pt(111) surface is investigated using thermal desorption (TDS), high resolution electron energy loss (HREELS) and ultraviolet photoelectron (UPS) spectroscopies. When submonolayer amounts of potassium are preadsorbed, the adsorption energy of CO increases from 25 to 36 kcal/mole, while substantial shifts in the site occupancy from the linear to the bridged site are observed. The CO stretching vibrational frequencies are shown to decrease continuously with either increasing potassium coverage or decreasing CO coverage. A minimum CO stretching frequency of 1400 cm^?1 is observed, indicative of a CO bond order of 1.5. The work function decreases by up to 4.5 eV at submonolayer potassium coverages, but then increases by 1.5 eV upon CO co-adsorption. The results indicate that the large adsorption energy, vibrational frequency and work function changes are due to molecular CO adsorption with a substantial charge donation from potassium through the platinum substrate and into the 2π¹_CO orbital.     

Interaction of Co with an Fe(111) surface

Adsorption of CO on Fe(111) below 300 K causes the appearance of three different non-dissociated species as distinguished by their CO stretch frequencies of about 1530 cm^-1 (a), 1800 cm^-1 (b), and 2000 cm^-1 (c). At T ? 220 K the b-state is first filled up and saturates after 1.5 L exposure; upon increasing the temperature it partly desorbs around 400 K and partly dissociates. Recombination of the C and O atoms followed by CO desorption takes place at about 800 K. Above 1.5 L exposure the a- and c-states are occupied simultaneously; in the thermal desorption spectrum in turn they show up as a relatively broad shoulder at ～ 340 K, which indicates similar adsorption energies for these two species. Saturation of the surface is reached after about 6 L exposure, which is paralleled by a continuous work function increase of up to Δφ = 1.6 eV. A high background intensity in the LEED pattern suggests substantial disorder in the adlayer. Evaluation of the TDS data yields about 2:1 population of the b- and (c + a)-states. The unusual low CO frequency of the a-state finds its analogues in reports on CO adsorption at stepped surfaces, as well as with complex compounds where the π-orbitals of the ligand directly interact with a neighboring metal atom. This species is therefore identified with adsorption in the “deep hollow” sites on the rather open Fe(111) surface. The b-state is tentatively attributed to the “shallow hollow” sites, and the c-state to adsorption on the “on top” sites.     

CHaracterization of CO binding sites on Rh{111} and Rh{331} surfaces by XPS and LEED: Comparison to EELS results

Changes in the nature of the binding site of chemisorbed CO on the Rh{111} and Rh{331} single crystal surfaces during adsorption and desorption have been monitored by X-ray Photoelectron Spectroscopy (XPS) and Low Energy Electron Diffraction (LEED). Two bonding states of molecular CO have been identified from the O 1s photoemission line. These states are assigned as atop and bridge-bonded species and are observed to be coverage and temperature dependent. On both surfaces atop sites are populated first and at higher CO coverages bridge sites are filled. On Rh{111} the bridge sites are filled at a CO coverage of θ_CO ～ 0.50 and their presence is correlated with a change in the LEED pattern. The presence of the step atoms on the Rh{331} surface markedly influenced the sequential filling of binding sites in comparison to that observed on the Rh{111} surface. A comparison of our data to previous Electron Energy Loss Spectroscopy (EELS) work on Rh{111} is in remarkable quantitative agreement with EELS peak heights.     

Ni(111)表面C原子吸附的密度泛函研究

基于密度泛函理论的第一性原理计算,对过渡金属Ni晶体与Ni (111)表面的结构和电子性质进行了研究, 并探讨了单个C原子在过渡金属Ni (111)表面的吸附以及两个C原子在Ni(111)表面的共吸附. 能带和态密度计算表明, Ni晶体及Ni (111)表面在费米面处均存在显著的电子自旋极化. 通过比较Ni (111)表面各位点的吸附能,发现单个C原子在该表面最稳定的吸附位置为第二层Ni原子上方所在的六角密排洞位, 吸附的第二个C原子与它形成碳二聚物时最稳定吸附位为第三层Ni原子上方所在的面心立方洞位. 电荷分析表明,共吸附时从每个C原子上各有1.566e电荷转移至相邻的Ni原子, 与单个C原子吸附时C与Ni原子间的电荷转移量(1.68e)相当. 计算发现两个C原子共吸附时在六角密排洞位和面心立方洞位的磁矩分别为0.059μ_B和 0.060μ_B,其值略大于单个C原子吸附时所具有的磁矩(0.017μ_B).     

Ni(111)表面一氧化碳和氢共吸附的密度泛函理论研究

本文用密度泛函理论(DFT)的总能计算研究了一氧化碳和氢原子在Ni(111)表面上p(2×2)共吸附系统的原子结构和电子态，结果表明CO和H原子分别被吸附于两个对角p(1×1)元胞的hcp和fcc位置.以氢分子和CO分子作为能量参考点，总吸附能为2.81 eV，相应的共吸附表面功函数φ为6.28 eV.计算得到的C—O，C—Ni和H—Ni的键长分别是1.19?, 1.96?和 1.71?，并且CO分子以C原子处于hcp的谷位与金属衬底原子结合.衬底Ni(111)的最外两层的晶面间距在吸附后的相对变化分别是 关键词： Fisher-Tropsch反应 催化作用 Ni(111) p(2×2)/(CO+H) 共吸附     

Substitutional adsorption of K on Fe(100)

The adsorption of potassium on Fe(100) was studied by time-of-flight forward scattering and recoiling spectroscopy (TOF-SARS), low energy electron diffraction (LEED) and Auger electron spectroscopy (AES). After heating to 650 K of the potassium saturated surface the formation of a p(3 × 3) potassium superstructure was observed by LEED. TOF-SARS experiments ruled out the adsorption of potassium in the on-top, bridge and four-fold hollow site. The only site which is in agreement with all experimental results is the substitutional site where K replaces an Fe atom of the topmost layer of the crystal. This is the first time a substitutional adsorption site has been found on a bcc surface. On an fcc surface such an adsorption site has been found recently for adsorption of sodium and potassium on Al(111).     

Site-specific core level spectroscopy of CO and NO adsorption on Pt(110)(1×2) and (1×1) surfaces

The adsorption of CO and NO on the (1×2) and (1×1) modifications of the Pt(110) surface was studied by x-ray photoemission spectroscopy, LEED and work-function change measurements. The O(1s) binding energy of adsorbed CO is site-specific and differentiates between on-top and bridge adsorbed species. CO adsorption on Pt(110)(1×2) at 120 K occurred sequentially into on-top and bridge sites yielding an orderedc(8×4) layer at the maximum coverage. At 300 K only on-top bonded CO was present after CO adsorption on the (1×2) surface. CO adsorption on the (1×1) surface at 120 K showed a transient bridge adsorbed CO and on-top CO at saturation, with an ordered (2×1)p1g1 LEED pattern. Heating the (2×1)p1g1 CO layer to 400 K also showed this transient bridge CO species. Work function changes generally correlated with the appearance of different CO species but were complex in detail. The findings for CO adsorption are consistent with the missing row model of the (1×2) surface.Parallel data for NO adsorption on (1×2) and (1×1) surfaces at 120 K were less informative than those for CO because O(1s) spectra showed single broad peaks. Peak contributions due to bridge and on-top bonded NO could be estimated.     

CO on Pd(110): determination of the optimal adsorption site

We present ab initio pseudo-potential plane-wave total-energy calculations for the geometric and electronic structure of the CO-covered Pd(110) surface. Our calculations were performed within the local-density approximation (LDA) of density functional theory (DFT). There has been some controversy as to whether CO prefers to adsorb at a bridge or on-top site when exposed to Pd(110). Total energy calculations for a CO monolayer adsorbed at the on-top and bridge adsorption sites revealed the bridge site adsorption to be favored by 0.59 eV per CO molecule. The preferential adsorption of CO to the bridge site was further corroborated by our band-structure calculations, with only the bridge site results being in good agreement with recent inverse photoemission experiments.     

CO and O coadsorption on Pt3Sn studied by DFT: Changes in the adsorptive properties of the surface with alloying and coverage

Adsorption of CO and coadsorption of O and CO on Pt₃Sn(1 1 1) was studied using periodic DFT calculations. Calculations were performed on Pt(1 1 1) by using the same set of parameters and their results were used as reference basis. The calculations showed that the most stable configuration with the minimum energy for coadsorption of CO and O is CO adsorbed atop Pt and O adsorbed on fcc Pt2Sn hollow site and that the decrease in the adsorption strength of the system at a total surface coverage of 0.5 ML is by 0.063 eV as a result of coadsorption, with respect to the adsorption of one species individually. Results show that the interaction between the adsorbed CO and O is short range on PtSn alloy, contrary to that on pure Pt, and this is mainly related to stronger Sn–O bonds compared to Pt–O bonds which eventually reduce the surface strain at the coadsorption structure. There is a pronounced effect of total surface concentration on the adsorption energy of coadsorbed species; the adsorption strength is not directly proportional to the surface coverage but is also related to the distribution of the coadsorbed species on the surface.     

Surface chemistry studied by in situ X-ray photoelectron spectroscopy

Time-dependent X-ray photoelectron spectroscopy is used to study the kinetics and dynamics of simple surface reactions. Combining high-resolution core level spectroscopy with a supersonic molecular beam in one experimental setup, processes such as the dissociative adsorption of methane on both Pt(111) and Ni(111), the coadsorption of water and CO on Pt(111), and the oxidation of CO on Pt(111) have been studied. In the case of methane, the observed vibrational fine structure in C 1s spectra is used to identify the adsorbed species (CH₃) and further thermal dehydrogenation steps. While simple dehydrogenation via CH is observed on Pt(111), a C–C coupling reaction to acetylene is found on Ni(111). In the coadsorbate phase, CO is found to be able to replace predosed water from the bilayer into multilayers. Water, in turn, leads to a site change of the CO molecules, which are preferably adsorbed at bridge sites in the presence of water, as opposed to on-top adsorption on clean Pt(111). For the truly bimolecular surface reaction, the CO oxidation on Pt(111), the ability of the molecular beam to create a relatively high CO pressure was found essential to study the kinetics of the basic step (CO+OCO₂) without influence of adsorption or diffusion rate. An activation energy of 0.53 eV and a preexponential factor of 5×10⁶ s^-1 are found. PACS 68.43.Mn; 79.60.Dp; 82.20.Pm     

Adsorption of oxygen on Au(111) by exposure to ozone

Atomic oxygen coverages of up to 1.2 ML may be cleanly adsorbed on the Au(111) surface by exposure to O₃ at 300 K. We have studied the adsorbed oxygen layer by AES, XPS, HREELS, LEED, work function measurements and TPD. A plot of the O(519 eV)/Au(239 eV) AES ratio versus coverage is nearly linear, but a small change in slope occurs at Θ_O=0.9 ML. LEED observations show no ordered superlattice for the oxygen overlayer for any coverage studied. One-dimensional ordering of the adlayer occurs at low coverages, and disordering of the substrate occurs at higher coverages. Adsorption of 1.0 ML of oxygen on Au(111) increases the work function by +0.80 eV, indicating electron transfer from the Au substrate into an oxygen adlayer. The O(1s) peak in XPS has a binding energy of 530.1 eV, showing only a small (0.3 eV) shift to a higher binding energy with increasing oxygen coverage. No shift was detected for the Au 4f_7/2 peak due to adsorption. All oxygen is removed by thermal desorption of O₂ to leave a clean Au(111) surface after heating to 600 K. TPD spectra initially show an O₂ desorption peak at 520 K at low Θ_O, and the peak shifts to higher temperatures for increasing oxygen coverages up to Θ_O=0.22 ML. Above this coverage, the peak shifts very slightly to higher temperatures, resulting in a peak at 550 K at Θ_O=1.2 ML. Analysis of the TPD data indicates that the desorption of O₂ from Au(111) can be described by first-order kinetics with an activation energy for O₂ desorption of 30 kcal mol⁻¹ near saturation coverage. We estimate a value for the Au–O bond dissociation energy D(Au–O) to be 56 kcal mol⁻¹.