Nuclear magnetic resonance in Ag-Pd alloys

Using the results of the self-consistent KKR CPA band calculation, the magnitudes of electron interactions in silver-rich Ag-Pd alloys are estimated from the experimental NMR data for ¹⁰⁹Ag, and Stoner's enhancement factor in the s-band spin susceptibility is found to be about 2.     

Photoemission study of oxygen chemisorption on tin

Photoemission measurements have been made at photon energies from 5–12 eV and at 21.2 eV on evaporated Sn films and the same films with varying room temperature exposure to oxygen. For hν ? 9 eV the quantum yield for Sn with exposures of as much as 4000 L oxygen (1 L = 1 Langmuir = 10^?6 Torr sec) differs only slightly from the clean metal. For hν ? 9 eV no change in yield is observed with oxygen exposure. The energy distribution of photoemitted electron (EDC's) from Sn with increasing exposure to oxygen above ? 20 L are characterized by the growth of two peaks which were not present in the EDC's for the clean metal, located 2.9 ± 0.1 eV and 4.8 ± 0.1 eV below the Fermi level. We associate this structure with the presence of SnO₂. No sharp resonance which could be associated with adsorbed oxygen was seen. Uniformly reduced emission from metallic Sn states and a Fermi level as sharp as for the clean metal is observed in the EDC's at all oxygen exposures. In addition, no change in work function with oxygen exposure was detected. The effects of oxygen saturate for exposures ? 4000 L. We suggest that under the conditions used in this experiment, the oxygen penetrates beneath the surface forming SnO₂ and leaving metallic Sn on the surface.     

Radiation induced chemisorption of oxygen on chromia

The effect of nuclear radiation on the chemisorption of oxygen on Cr₂O₃, Cr₂O₃-Al₂O₃ and Cr₂O₃-SnO₂ catalysts has been studied. An iodometric method was used to measure the amount of chemisorbed oxygen; simultaneously the increase in the catalytic activity of the catalyst in the decomposition of H₂O₂ was determined. It was found that the radiation present within a nuclear reactor promotes the chemisorption of oxygen on chromia (either pure or supported on Al₂O₃ or SnO₂) at temperatures at which such a chemisorption does not normally occur. The radiochemisorption of oxygen on chromia increases with the degree of dispersion of chromia on Al₂O₃ or SnO₂ and is accompanied by an increased catalytic activity of this catalyst in the decomposition reaction of H₂O₂. It seems that the radiochemisorption is largely due to the action of γ-rays and fast neutrons on the gas.     

Surface composition of native gold and Ag/Au alloys

The surface composition of Ag/Au alloys has been studied by X-ray photoelectron spectroscopy (XPS). Surface segregation of Ag is observed, particularly for alloys having low Ag content. The content of Ag in the first surface monolayer is in accordance with data from ion scattering and with a theoretical model for segregation in ordered solutions. The surface of native gold was found to be enriched with silver in the case of mine gold, and the degree of segregation was significantly higher than for an alloy having similar bulk composition. The surface of mine gold taken from an oxidized zone contained less silver than did that of usual mine gold. The surface of placer gold was depleted of silver as compared to the bulk. These data show the surface composition of native gold to differ markedly from that of an alloy having the same bulk Ag content, and to depend on the genesis of the native gold sample.     

Theory of chemisorption of hydrogen on transition metals and their alloys

A theoretical discussion is given of the changes in the heat of chemisorption of a hydrogen atom upon alloying a group-VIII metal with a group-IB metal. The emphasis is on two concepts: the ensemble effect and the ligand effect. The ensemble effect ascribes the changes in the heat of chemisorption primarily to changes in the geometry of the adsorption complex, whereas the ligand effect also takes into account changes in bond strength due to a different intrinsic activity of the bonding metal atoms.     

Calculation of chemisorption energies of oxygen on narrow-gap semiconductors

Newns' self-consistent model for hydrogen chemisorption on transition metals is extended to calculate the chemisorption energy ΔE of oxygen on Si, Ge and III–V compounds. ΔE is found to depend on the widths of the energy gap and valence band, the crystal work function and the crystal plane, |ΔE₍₁₀₀₎|>|ΔE₍₁₁₁₎|. In general, larger ΔE's are associated with wider energy gaps.     

Magnetic and infrared study of CO chemisorption on silica supported nickel-copper alloys

CO adsorption at room temperature on Ni-Cu alloys supported on SiO₂ is studied by two complementary techniques, infra-red spectroscopy and magnetic methods (saturation magnetization). The bond number between CO and the metallic surface calculated from magnetic data decreases from 1.8 to 1 as the Cu content increases. Two bands attributed to CO bonded to Ni are observed (the A band in the 2000–2050 cm^?1 region, and the B band in the 1950–1900 cm^?1 region). A small band assigned to CO bonded to Cu is also detected. As Cu content increases, the intensity of the B band decreases, and a noticeable and continuous frequency shift of the three bands is observed. Experimental results are fully accounted for assuming that: (i) two adsorbed species of CO on Ni, a monodentate and a bridged species (with small amounts of other multicentered species) are formed, as suggested by Eischens and Pliskin; (ii) dilution of Ni by Cu decreases the relative abundance of the bridged (and multicentered) species for some geometric reasons previously invoked by Soma-Noto and Sachtler; (iii) surface complexes are formed between CO and Ni; however Ni remains in its metallic state. The surface complex is sensitive to the electronic environment of the metallic atom, with a frequency shift of the three infra-red bands upon alloying as a consequence.     

Surface vibrational studies of organic molecule chemisorption on silicon

We discuss the most interesting results of an extensive research program on the chemisorption properties of organic molecules on semiconductor substrates. Specific systems discussed in detail are benzene, pyridine and thiophene on cleaved Si(111). In particular, we find that the chemisorption of benzene or pyridine on room-temperature substrates leads to the breaking of C-H bonds in the absorbed molecules and to the formation of Si-C bonds.     

Surface composition changes caused by Ar ion bombardment of Au-Ni alloys

Surface composition changes caused by 1 keV Ar ion bombardment of a series of Au-Ni alloys at room temperature were studied. Using 11 combinations of different energy Auger spectra, the variation of the composition with depth from 0.4 to 1.5 nm in a bombarded Au-Ni alloy was obtained. We found that a drastic variation in concentration took place within the first few layers. This is evidently indicating that a bombardment-induced Gibbsian segregation exists in the Au-Ni system. We also found that the degree of gold depletion at the second layer depended strongly on the bulk composition, thus this depletion became slight as the gold content in alloy was high. In addition, we have roughly estimated the concentration of Au at the topmost layer of a bombarded Au-Ni alloy and found that this value tentatively might be smaller than the bulk one. This result differs from two known examples: C(Au, top) > C(Au, bulk) in a bombarded Au-Cu alloy and C(Cu, top) = C(Cu, bulk) in a bombarded Cu-Ni alloy. Comparing our experimental results with a recent theory presented by Kelly, we suggest that a more sophisticated theory should take this new phenomenon into account.     

Tight-binding Ising-model study of chemisorption effects on surface segregation in transition-metal alloys

The tight-binding Ising model is generalized for the system consisting of a transition-metal alloy with chemisorbed adatoms. The effect of chemisorption on the surface segregation is calculated within the scope of a semi-infinite linear chain model for hydrogen chemisorbed on a Cu-Ni alloy. The charge-neutrality condition is incorporated into the model and its effect on the calculated surface segregation is demonstrated.     

Electronic theory of the chemisorption effect on surface segregation in transition-metal alloys

The tight-binding Ising model generalized for a system consisting of a transition-metal alloy with chemisorbed adatoms is used to calculate the effect of hydrogen chemisorption on surface segregation in a Cu---Ni alloy. The simple model of chemisorption and of the band structure of the alloy is assumed. The charge-neutrality condition is incorporated into the model.     

Theoretical study of oxygen chemisorption on zinc surface by cluster models

Theoretical calculations by DV-Xα-MO have been performed for clusters representing a Zn(0001) surface with oxygen. The calculated DOS is in good agreement with the experimental UPS spectra found by Briggs or by Abbati et al. A large amount of electron flow from Zn atoms into the oxygen atom occurs and this causes (1) a remarkable upward shift of the oxygen 2p level and (2) formation of an unoccupied level near the highest occupied level. The bonds between the oxygen 2p and the zinc 4s or 4p orbitals have a strong bonding character, and the contribution of the zinc 3d orbital to the Zn-O bond is not important.     

Surface sensitive spectroscopic study of the interaction of oxygen with Al(111) - low temperature chemisorption and oxidation

The interaction of an atomically clean Al(111) surface with O₂ has been studied using a combination of electron energy loss spectroscopy (EELS) and Auger spectroscopy (AES). Oxygen dissociatively adsorbs and occupies both surface and subsurface binding sites under all exposure conditions in the temperature range 122–700 K. Surface sites are preferentially occupied at low exposures, while higher exposures increasingly favor population of subsurface sites. Studies of O₂ adsorption at temperatures as low as 131 K have shown that formation of Al₂O₃ occurs at high oxygen exposures. The Al₂O₃ produced exhibits a 54 eV Auger transition and a characteristic vibrational spectrum with loss features at 430, 645, and 880 cm⁻¹. Argon ion bombardment of thin monolayer level Al₂O₃ layers leads to preferential loss of Al₂O₃ and a reduction in the subsurface-to-surface oxygen ratio. Electron bombardment of similar, thin Al₂O₃ layers is ineffective in inducing desorption of surface species, whereas thick Al₂O₃ layers are strongly influenced by electron bombardment, as judged from AES behavior. Qualitative models for O₂ adsorption, oxidative annealing, and damage by ion and electron bombardment are given.     

The process of oxygen chemisorption on the Si(111) surface

The chemisorption of oxygen on the Si(111) surface has been studied by the ASED-MO method. Three steps of the initial oxidation process have been proposed. The first step is molecular oxygen chemisorption. The second step is that of dissociated oxygen chemisorption in which the atomic short bridge site (between the first layer and second layer silicon atoms) can be occupied only after the saturation of the dangling bonds of the surface silicon with oxygen. The third step is the diffusion of atomic oxygen from the short bridge positions into the bulk of silicon to form an SiO₂ film. For molecular chemisorption, both the peroxy vertical and peroxy bridge models are possible although the peroxy vertical model is the more stable. The dissociated atomic oxygen can chemisorb for both the on-top and the short bridge models. Our results can explain, and are consistent with, most experimental results.     

氧原子在不同过渡金属表面吸附性质的比较研究

采用第一性原理方法对O原子在过渡金属Ir(100)表面吸附能和电子结构随覆盖度变化进行了理论研究,并与类似体系结果进行对比分析.研究结果表明:氧原子在不同过渡金属表面吸附强弱与金属表面d态电子结构密切相关,且在不同过渡金属(111)表面氧原子吸附能与Pt(111)表面的氧原子吸附能拟合结果呈线性关系.