Reactivity of 3-hexyne on oxygen modified Ru(0 0 1) surfaces: Observation of oxametallacycles by RAIRS

The chemical behaviour of 3-hexyne on oxygen modified Ru(0 0 1) surfaces has been analysed under ultrahigh-vacuum, using reflection-absorption infrared spectroscopy (RAIRS). The effects of oxygen coverage, 3-hexyne exposure and adsorption temperature were studied. Two modified Ru(0 0 1) surfaces were prepared: Ru(0 0 1)-(2 × 2)-O and Ru(0 0 1)-(2 × 1)-O that correspond to oxygen coverages (θ_O) of 0.25 and 0.5 ML, respectively. The striking result is the direct bonding to an O atom when the modified surfaces are exposed to a very low dose (0.2 L) of 3-hexyne at low temperature (100 K). For θ_O = 0.25 ML, an unsaturated oxametallacycle [Ru-O-C(C₂H₅)C(C₂H₅)-Ru] is proposed, identified by RAIRS for the first time, through the νCC and νCO modes. Further decomposition at 110 K yields smaller oxygenated intermediates, such as acetyl [μ₃-η²(C,O)-CH₃CO], co-adsorbed with a small amount of carbon monoxide and non-dissociated species. The temperature at which a fraction of molecules undergoes complete C-C and C-H bond breaking is thus much lower than on clean Ru(0 0 1). The ultimate decomposition product observed by RAIRS at 220 K is methylidyne [CH]. Another key observation was that the adsorption temperature is not determinant of the reaction route, contrarily to what occurs on clean Ru(0 0 1): even when 3- hexyne strikes the surface at a rather high temperature (220 K), the multiple bond does not break completely. For θ_O = 0.5 ML, a saturated oxametallacycle [Ru-O-CH(C₂H₅)-CH(C₂H₅)-Ru] is also proposed at 100 K, identified by the ν_asO-C-C (at 1043 cm⁻¹) and ν_sO-C-C (at 897 cm⁻¹) modes, showing that some decomposition with C-H bond breaking occurs. For this oxygen coverage, the reaction temperatures are lower, and the intermediate surface species are less stable.     

Morphological change of D2O layers on Ru(0 0 0 1) probed with He atom scattering

The morphological change of D₂O layers on a Ru(0 0 0 1) surface has been investigated on the basis of He atom scattering. With the increase of D₂O exposure on Ru(0 0 0 1) at 111 K, the intensity of a specularly reflected He beam continuously decreases up to the exposure of 1.0 L (Langmuir). At the D₂O coverage of 1.0 adsorbed layer (∼1.5 L), which is characterized by temperature-programmed desorption measurements, the formation of the (√3 × √3)R30° superstructure as a result of the diffusion of D₂O on the surface was confirmed by He atom diffraction. With the further increase of D₂O exposure, at 2-3 adsorbed layers, the disordered structure was found to be on the surface at 111 K. The morphological change of the disordered layers was observed during annealing, and discussed in detail.     

Growth and thermal evolution of submonolayer Pt films on Ru(0 0 0 1) studied by STM

The growth of submonolayer Pt on Ru(0 0 0 1) has been studied with scanning tunneling microscopy. We focus on the island evolution depending on Pt coverage θ_Pt, growth temperature T_G and post-growth annealing temperature T_A. Dendritic trigonal Pt islands with atomically rough borders are observed at room temperature and moderate deposition rates of about 5 × 10⁻⁴ ML/s. Two types of orientation, rotated by 180° and strongly influenced by minute amounts of oxygen are observed which is ascribed to nucleation starting at either hcp or fcc hollow sites. The preference for fcc sites changes to hcp in the presence of about one percent of oxygen. At lower growth temperatures Pt islands show a more fractal shape. Generally, atomically rough island borders smooth down at elevated growth temperatures higher than 300 K, or equivalent annealing temperatures. Dendritic Pt islands, for example, transform into compact, almost hexagonal islands, indicating similar step energies of A- and B-type of steps. Depending on the Pt coverage the thermal evolution differs somewhat: While regular islands on Ru(0 0 0 1) are formed at low coverages, vacancy islands are observed close to completion of the Pt layer.     

Surface structure of K/Pd(1 0 0) and the effect of H coadsorption: Density functional theory calculations

We have performed density-functional theory calculations to study the atomic structure of the K/Pd(1 0 0)-p(2 × 2) and -c(2 × 2) surfaces formed at 0.25 ML and 0.5 ML, respectively. We find that K atoms prefer the hollow site with the K adsorption height 2.44 Å for p(2 × 2) and 2.50 Å c(2 × 2). The first interlayer spacing (d₁₂) of the Pd(1 0 0) substrate appears slightly contracted from the bulk value as Δd₁₂ = −0.8% and −0.3% for p(2 × 2) and c(2 × 2), respectively. The calculated contraction Δd₁₂ = −0.3% for c(2 × 2) is not in accord with the expansion Δd₁₂ = +1.3% reported by a low-energy electron diffraction (LEED) study. As the origin of this difference, a possibility of hydrogen contamination of the surface sample used in the LEED study is suggested: Our calculations show that the d₁₂ of K/Pd(1 0 0)-c(2 × 2) increases linearly with the coverage of H coadsorption, which leads to an estimation for the H coverage of the surface sample as 0.1-0.4 ML.     

Anomalous adsorption of Cs on Pt(1 1 1)

The adsorption of Cs on Pt(1 1 1) surfaces and its reactivity toward oxygen and iodine for coverages θ_Cs?0.15 is reported. These surfaces show unusual “anomalous” behavior compared to higher coverage surfaces. Similar behavior of K on Pt(1 1 1) was previously suggested to involve incorporation of K into the Pt lattice. Despite the larger size of Cs, similar behavior is reported here. Anomalous adsorption is found for coverages lower than 0.15 ML, at which point there is a change in the slope of the work function. Thermal Desorption Spectroscopy (TDS) shows a high-temperature Cs peak at 1135 K, which involves desorption of Cs⁺ from the surface.The anomalous Cs surfaces and their coadsorption with oxygen and iodine are characterized by Auger Electron Spectroscopy (AES), TDS and Low Electron Energy Diffraction (LEED). Iodine adsorption to saturation on Pt(1 1 1)(anom)-Cs give rise to a sharp LEED pattern and a distinctive work function increase. Adsorbed iodine interacts strongly with the Cs and weakens the Cs-Pt bond, leading to desorption of Cs_xI_y clusters at 560 K. Anomalous Cs increases the oxygen coverage over the coverage of 0.25 ML found on clean Pt. However, the Cs-Pt bond is not significantly affected by coadsorbed oxygen, and when oxygen is desorbed the anomalous cesium remains on the surface.     

Oxygen adsorption and oxidation reactions on Au(2 1 1) surfaces: Exposures using O2 at high pressures and ozone (O3) in UHV

Nanosized gold particles supported on reducible metal oxides have been reported to show high catalytic activity toward CO oxidation at low temperature. This has generated great scientific and technological interest, and there have been many proposals to explain this unusual activity. One intriguing explanation that can be tested is that of Nørskov and coworkers [Catal. Lett. 64 (2000) 101] who suggested that the “unusually large catalytic activity of highly-dispersed Au particles may in part be due to high step densities on the small particles and/or strain effects due to the mismatch at the Au-support interface”. In particular, their calculations indicated that the Au(2 1 1) stepped surface would be much more reactive towards O₂ dissociative adsorption and CO adsorption than the Au(1 1 1) surface. We have now studied the adsorption of O₂ and O₃ (ozone) on an Au(2 1 1) stepped surface. We find that molecular oxygen (O₂) was not activated to dissociate and produce oxygen adatoms on the stepped Au(2 1 1) surface even under high-pressure (700 Torr) conditions with the sample at 300-450 K. Step sites do bind oxygen adatoms more tightly than do terrace sites, and this was probed by using temperature programmed desorption (TPD) of O₂ following ozone (O₃) exposures to produce oxygen adatoms up to a saturation coverage of θ_O = 0.90 ML. In the low-coverage regime (θ_O ? 0.15 ML), the O₂ TPD peak at 540 K, which does not shift with coverage, is attributed to oxygen adatoms that are bound at the steps on the Au(2 1 1) surface. At higher coverages, an additional lower temperature desorption peak that shifts from 515 to 530 K at saturation coverage is attributed to oxygen adsorbed on the (1 1 1) terrace sites of the Au(2 1 1) surface. Although the desorption kinetics are likely to be quite complex, a simple Redhead analysis gives an estimate of the desorption activation energy, E_d, for the step-adsorbed oxygen of 34 kcal/mol and that for oxygen at the terraces near saturation coverage of 33 kcal/mol, values that are similar to others reported on Au surfaces. Low Energy Electron Diffraction (LEED) indicates an oxygen-induced step doubling on the Au(2 1 1) surface at low-coverages (θ_O = 0.08-0.17 ML) and extensive disruption of the 2D ordering at the surface for saturation coverages of oxygen (θ_O ? 0.9 ML). Overall, our results indicate that unstrained step sites on Au(2 1 1) surfaces of dispersed Au nanoparticles do not account for the novel reactivity of supported Au catalysts for CO oxidation.     

Interaction of CO with atomically well-defined PtxRuy/Ru(0 0 0 1) surface alloys

The interaction of CO with structurally well-defined Pt_xRu_y surface alloys supported on Ru(0 0 0 1) was investigated by thermal desorption spectroscopy and infrared reflection-absorption spectroscopy. The surface composition and the distribution of the surface atoms were controlled by high resolution scanning tunneling microscopy. On these surfaces, which have a nearly random distribution of the two surface species, the adsorption (and desorption) of CO is strongly modified compared to the pure elemental surfaces, by strain effects and electronic ligand effects. CO adsorbs exclusively in a linear configuration on Pt and Ru atoms for all surfaces investigated. The adsorption energy of CO is lowered on the alloy surfaces with respect to both Pt(1 1 1) and Ru(0 0 0 1), similar as for pseudomorphic monolayer Pt films. For both Pt and Ru sites the adsorption strength decreases with increasing Pt concentration.     

The mechanism of amine formation on Si(1 0 0) activated with chlorine atoms

The dissociation of NH₃ on a Si(1 0 0) surface activated with Cl atoms was investigated using X-ray photoelectron spectroscopy. Gas phase UV-Cl₂ (0.1-10 Torr Cl₂ for 10-600 s under 1000 W Xe lamp illumination) completely replaced the H-termination on aqueous-cleaned Si(1 0 0) with 0.82 ± 0.06 ML of Cl at 298 K. A single spin-orbit split Cl 2p doublet indicated that the Cl atoms were bound to Si dimer atoms, forming silicon monochloride (Cl-Si-Si-Cl). Exposing the Cl-terminated surface at 348 K to NH₃ (1-1000 Torr for 5-60 min) replaced one Cl atom with one N atom up to a coverage of 0.33 ± 0.02 ML. Cl atoms lowered the activation energy barrier for reaction to form a primary amine (Si-NH₂). Oxygen was coadsorbed due to competition by H₂O contamination. The presence of Cl on the surface even after high NH₃ exposures is attributed to site blocking and electrostatic interactions among neighboring Cl-Si-Si-NH₂ moieties. The results demonstrate a low temperature reaction pathway for depositing N-bearing molecules on Si surfaces.     

Mixed water/OH structures on Pd(1 1 1)

Chemisorbed O and water react on Pd(1 1 1) at low temperatures to form a mixed OH/H₂O layer with a (√3 × √3)R30° registry. Reaction requires at least two water molecules to each O before the (2 × 2)O islands are consumed, the most stable OH/water structure being a (OH + H₂O) layer containing 0.67 ML of oxygen, formed by the reaction 3H₂O + O → 2(H₂O + OH). This structure is stabilised compared to pure water structures, decomposing at 190 K as OH recombines and water desorbs. The (√3 × √3)R30° − (OH + H₂O) phase cannot be formed by O/H reaction and is distinct from the (√3 × √3)R30° structure formed by O/H coadsorption below 200 K. Mixed OH/water structures do not react with coadsorbed H below 190 K on Pd(1 1 1), preventing this phase catalyzing the low temperature H₂/O₂ reaction which only occurs at higher temperatures.     

Adsorption and reaction of methanethiol on the Ru(0 0 0 1)-p(2 × 2)O surface: A TPD and XPS study

Methanethiol adsorbed on Ru(0 0 0 1)-p(2 × 2)O has been studied by TPD and XPS. The dissociation of methanethiol to methylthiolate and hydrogen at 90 K is evidenced by the observation of hydroxyl and water. The saturation coverage of methylthiolate is ∼0.15 ML, measured by both XPS and TPD. A detailed analysis suggests that only the hcp-hollow sites have been occupied. Upon annealing the surface, water and hydroxyl desorb from the surface at ∼210 K. Methylthiolate decomposes to methyl radical and atomic sulphur via C-S cleavage between 350 and 450 K. Some methyl radicals (0.05 ML) have been transferred to Ru atoms before they decompose to carbon and hydrogen. The rest of methyl radicals desorb as gaseous phase. No evidence for the transfer of methyl radical to surface oxygen has been found.     

Growth mode and electronic structure of Au nano-clusters on NiO(0 0 1) and TiO2(1 1 0)

The growth mode and electronic structure of Au nano-clusters grown on NiO and TiO₂ were analyzed by reflection high-energy electron diffraction, a field-emission type scanning electron microscope, medium energy ion scattering and photoelectron spectroscopy. Au was deposited on clean NiO(0 0 1)-1 × 1 and TiO₂(1 1 0)-1 × 1 surfaces at room temperature with a Knudsen cell at a rate of 0.25-0.35 ML/min (1 ML = 1.39 × 10¹⁵ atoms/cm²:Au(1 1 1)). Initially two-dimensional (2D) islands with thickness of one Au-atom layer grow epitaxially on NiO(0 0 1) and then neighboring 2D-islands link each other to form three-dimensional (3D)-islands with the c-axis oriented to the [1 1 1] direction. The critical size to form 3D-islands is estimated to be about 5 nm². The shape of the 3D-islands is well approximated by a partial sphere with a diameter d and height h ranging from 2.0 to 11.8 nm and from 0.95 to 4.2 nm, respectively for Au coverage from 0.13 to 4.6 ML. The valence band spectra show that the Au/NiO and Au/TiO₂ surfaces have metallic characters for Au coverage above 0.9 ML. We observed Au 4f spectra and found no binding energy shift for Au/NiO but significant higher binding energy shifts for Au/TiO₂ due to an electron charge transfer from Au to TiO₂. The work function of Au/NiO(0 0 1) gradually increases with increase in Au coverage from 4.4 eV (NiO(0 0 1)) to 5.36 eV (Au(1 1 1)). In contrast, a small Au deposition(0.15 to 1.5 ML) on TiO₂(1 1 0) leads to reduction of the work function, which is correlated with an electron charge transfer from Au to TiO₂ substrate.     

Alloy formation of Co/Ni/Pt(1 1 1)

The initial growth and alloy formation of ultrathin Co films deposited on 1 ML Ni/Pt(1 1 1) were investigated by Auger electron spectroscopy (AES), low energy electron diffraction (LEED), and ultraviolet photoelectron spectroscopy (UPS). A sequence of samples of d_Co Co/1 ML Ni/Pt(1 1 1) (d_Co = 1, 2, and 3 ML) were prepared at room temperature, and then heated up to investigate the diffusion process. The Co and Ni atoms intermix at lower annealing temperature, and Co-Ni intermixing layer diffuses into the Pt substrate to form Ni-Co-Pt alloys at higher annealing temperature. The diffusion temperatures are Co coverage dependent. The evolution of UPS with annealing temperatures also shows the formation of surface alloys. Some interesting LEED patterns of 1 ML Co/1 ML Ni/Pt(1 1 1) show the formation of ordered alloys at different annealing temperature ranges. Further studies in the Curie temperature and concentration analysis, show that the ordered alloys corresponding to different LEED patterns are Ni_xCo_1−xPt and Ni_xCo_1−xPt₃. The relationship between the interface structure and magnetic properties was investigated.     

Theoretical study of hydrogen adsorption on the GaN(0 0 0 1) surface

Ab initio density functional theory, using the B3LYP hybrid functional with all-electron basis sets, has been applied to the adsorption of H on the (0 0 0 1) surface of wurtzite GaN. For bulk GaN, good agreement is obtained with photoemission and X-ray emission data for the valence band and for the Ga 3d and N 2s shallow core levels. A band gap of E_g = 4.14 eV is computed vs the experimental value (at 0 K) of 3.50 eV. A simple model, consisting of a (2 × 2) structure with 3/4-monolayer (ML) of adsorbed H, is found to yield a density of states in poor agreement with photoemission data for H adsorbed on surfaces prepared by ion bombardment and annealing. A new model, consisting of co-adsorbed Ga (1/4 ML) and H (1/2 ML), is proposed to account for these data.     

Spin-pumping-enhanced magnetic damping in ultrathin Cu(0 0 1)/Co/Cu and Cu(0 0 1)/Ni/Cu films

The influence of the Cu capping layer thickness on the spin pumping effect in ultrathin epitaxial Co and Ni films on Cu(0 0 1) was investigated by in situ ultrahigh vacuum ferromagnetic resonance. A pronounced increase in the linewidth is observed at the onset of spin pumping for capping layer thicknesses d_Cu larger than 5 ML, saturating at d_Cu = 20 ML for both systems. The spin mixing conductance for Co/Cu and Ni/Cu interfaces was evaluated.     

Density functional study of oxygen adsorption on the Mg3Nd (0 0 1) surface

The adsorption of oxygen atoms on Mg₃Nd (0 0 1) surface was studied based on density function theory (DFT), in which the exchange-correlation potential was chosen as the generalized gradient approximation (GGA) in the Perdew and Wang (PW91). The most preferred adsorption position was at the top-hollow site. Upon the optimization on top-hollow site with different coverage, it was found that the adsorption energy decreased with oxygen coverage. The density of states analysis showed that obvious charge transfer took place between O atom and the nearest Nd atom and chemical bond formed between O atom and the nearest Nd atom after O adsorption. The result of surface energy as a function of chemical potential change of oxygen indicated the clean Mg₃Nd (0 0 1) surface was easy to adsorb oxygen and form 1.00 ML surface.     

Reaction of water with Ce-Au(1 1 1) and CeOx/Au(1 1 1) surfaces: Photoemission and STM studies

This article reports photoemission and STM studies for the adsorption and dissociation of water on Ce-Au(1 1 1) alloys and CeO_x/Au(1 1 1) surfaces. In general, the adsorption of water at 300 K on disordered Ce-Au(1 1 1) alloys led to O-H bond breaking and the formation of Ce(OH)_x species. Heating to 500-600 K induced the decomposition or disproportionation of the adsorbed OH groups, with the evolution of H₂ and H₂O into gas phase and the formation of Ce₂O₃ islands on the gold substrate. The intrinsic Ce ↔ H₂O interactions were explored by depositing Ce atoms on water multilayers supported on Au(1 1 1). After adsorbing Ce on ice layers at 100 K, the admetal was oxidized immediately to yield Ce³⁺. Heating to room temperature produced finger-like islands of Ce(OH)_x on the gold substrate. The hydroxyl groups dissociated upon additional heating to 500-600 K, leaving Ce₂O₃ particles over the surface. On these systems, water was not able to fully oxidize Ce into CeO₂ under UHV conditions. A complete Ce₂O₃ → CeO₂ transformation was seen upon reaction with O₂. The particles of CeO₂ dispersed on Au(1 1 1) did not interact with water at 300 K or higher temperatures. In this respect, they exhibited the same reactivity as does a periodic CeO₂(1 1 1) surface. On the other hand, the Ce₂O₃/Au(1 1 1) and CeO_2−x/Au(1 1 1) surfaces readily dissociated H₂O at 300-500 K. These systems showed an interesting reactivity for H₂O decomposition. Water decomposed into OH groups on Ce₂O₃/Au(1 1 1) or CeO_2−x/Au(1 1 1) without completely oxidizing Ce³⁺ into Ce⁴⁺. Annealing over 500 K removed the hydroxyl groups leaving behind CeO_2−x/Au(1 1 1) surfaces. In other words, the activity of CeO_x/Au(1 1 1) for water dissociation can be easily recovered. The behavior of gold-ceria catalysts during the water-gas shift reaction is discussed in light of these results.     

Interaction between chemisorbed N2 and Li promoter atoms: A comparison between the stepped Ru(1 0 9) and the atomically smooth Ru(0 0 1) surfaces

We present a direct side-by-side comparison of the interaction of Li atoms and N₂ molecules on the atomically stepped Ru(1 0 9) single crystal surface and on the atomically smooth Ru(0 0 1) single crystal surface using infrared reflection absorption spectroscopy (IRAS) and temperature programmed desorption (TPD). At low adsorbate coverages there is spectroscopic evidence for the formation of a Li_x(N₂)_y complex on the Ru(1 0 9) surface, whereas no such complex is observed on the Ru(0 0 1) surface. This complex is due to local interactions between an adsorbed Li atom and N₂ adsorbed on the atomic steps of Ru(1 0 9). The short range interaction near the atomic steps is characterized by the development of several highly red-shifted ν(N₂) modes in the region of ∼2130 cm⁻¹ in the IR spectra. Adsorbed N₂ molecules on both Ru(1 0 9) and Ru(0 0 1) also are influenced by the long range electrostatic field produced by Li adsorbate atoms, causing a red shift in the uncomplexed N₂ species, which monotonically increases as the Li coverage in increased. On the Ru(0 0 1) surface, small coverages of N₂ influenced by the long range effect of Li are initially chemisorbed parallel to the surface resulting in the absence of infrared activity. In addition we have also found that Li does not cause N-N bond scission on Ru(0 0 1) below 250 K.     

Atom geometry of nanostructured Fe films grown on c(2 × 2)-N/Cu(1 0 0) surface: An investigation by X-ray absorption spectroscopy with multishell analysis

We investigated the growth of Fe nanostructured films on c(2 × 2)-N/Cu(1 0 0) surface with Fe K-edge X-ray absorption fine structure (XAFS) in the near edge and in the extended energy region. The high photon flux of the incident X-rays allowed us to perform multishell analysis of the XAFS oscillations for Fe coverage Θ_Fe < 1 ML. This data analysis yields a detailed investigation of the atom geometry and some insights in the film morphology. At Θ_N < 0.5 ML (N saturation coverage) there is absence of contribution to XAFS from N atoms. First shell analysis of linearly polarized XAFS gives Fe-Fe (or Fe-Cu) bond length values varying between R₁ = 2.526 ± 0.006 Å at the highest Fe coverage (3 ML ) and R₁ = 2.58 ± 0.01 Å at Θ_Fe = 0.5 ML, Θ_N = 0.3 ML, with incidence angle Θ = 35°. These values are different from the case of bcc Fe (R = 2.48 Å), and compatible with fcc Fe (R₁ = 2.52 Å) and fcc Cu (R₁ = 2.55 Å). At the Fe lowest coverage (Θ_Fe = 0.5 ML) the dependence of R₁ on the incidence angle indicates expansion of the outmost layer. Near edge spectra and multishell analysis can be well reproduced by fcc geometry with high degree of static disorder. At N saturation pre-coverage (Θ_N = 0.5 ML) the XAFS analysis has to keep into account the Fe-N bonding. The results suggest two different adsorption sites: one with Fe in a fcc hollow site, surrounded by other metal atoms as nearest neighbours, and one resulting from an exchange with a Cu atom underneath the N layer.     

Surface morphology of epitaxial lattice-matched Ba0.7Sr0.3O on Si(0 0 1) and vicinal Si(0 0 1)-4°[1 1 0] substrates

Exploring ways for self-organized structuring of insulating thin films, we investigated the possibility to produce replicas of step trains, given by a vicinal Si(0 0 1)-4°[1 1 0] surface, in layers of crystalline and perfectly lattice-matched Ba_0.7Sr_0.3O. For this purpose, we carried out high-resolution spot profile analyses in low-energy electron diffraction (SPA-LEED) both on flat Si(0 0 1) and on Si(0 0 1)-4°[1 1 0]. Oxide layers were generated by evaporating the metals in oxygen ambient pressure with the sample at room temperature. Our G(S) analysis of these mixed oxide layers reveals a strong influence of local compositional fluctuations of Sr and Ba ions and their respective scattering phases, which appears as an unphysically large variation of layer distances. Nevertheless, we are able to show that quite smooth and closed oxide films are obtained with an rms roughness of about 1 ML. These Ba_0.7Sr_0.3O films directly follow the step train of Sr-modified vicinal Si surfaces that form (1 1 3) oriented facets after adsorption of a monolayer of Sr. This proves that self-organized structuring of insulating films can indeed be an effective method.     

First-principles study on the catalytic role of Ag in the oxygen adsorption of LaMnO3(0 0 1) surface

In the present paper, the catalytic role of Ag in the oxygen adsorption of LaMnO₃(0 0 1) surface has been theoretically investigated using first-principles calculations based on the density functional theory (DFT) and pseudopotential method. The O₂ adsorption energy is larger for the vertical adsorption and the covalent bond was formed between O₂ molecule and surface Mn. The calculation of electronic properties of interaction between Ag atom and LaMnO₃(0 0 1) surface demonstrates that the most stable position for Ag adsorption is hollow site. The O₂ adsorption energy dramatically increased from 0.298 eV to 1.108 eV due to Ag pre-adsorbed. It is Ag pre-adsorbed that facilitates O₂ adsorption on surface. The bond length and bond population of O₂ molecule indicate that Ag atom facilitates O₂ molecule dissociative adsorption. The Ag atom strengthens LaMnO₃(0 0 1) substrate activity and activity center was formed on surface, which enhances the electrocatalytic activity of LaMnO₃ as solid oxide fuel cells cathode material at low temperature.