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1.
In the course of experiments that included Auger electron spectroscopy (AES) and high-resolution electron energy loss spectroscopy (HREELS) on cation exchange at benzoquinone sulfonate chemisorbed on a Pd(111) electrode, it was found that, whereas the AES spectra remained invariant as the counter cation was varied from H+ to K+ to Cs+, profound changes occurred in the HREELS spectra. Specifically, the intensity of the spectral features decreased noticeably when H+ was replaced with K+. And, when the K+ ions were exchanged with Cs+, nothing but a flat-line (dead) spectrum was observed; even the elastic peak was completely attenuated. When the Cs+ ions were displaced by protons, the initial undiminished spectrum was fully restored. This outcome, while unrelated to cation-exchange selectivity, is of exceptional significance in surface electron spectroscopy. It appears that the positive ions on the surface attracted the low-energy incident electrons such that backscattering towards the energy analyzer was hindered; partially by K+ but totally by the larger Cs+ ion. The use of HREELS to examine the molecular integrity of chemisorbed anionic species must thus take cognizance of the possibility that the counter cation chosen to preserve interfacial-layer electroneutrality can have a profound effect. To circumvent such complication, low-valent and small-radii cations will have to be employed. In addition, although subject to instrument limitations, higher incident-electron energies could be adopted. AES, with incident-electron energies in the kV range, is impervious to the presence of counter cations. 相似文献
2.
U. Falke 《Fresenius' Journal of Analytical Chemistry》1994,349(1-3):241
Transmission EELS measurements have been carried out on a-C:H films deposited by ion plating from acetone or n-hexane plasma using various substrate potentials. The calculated dielectric functions show low optical absorption in the range of 4 eV to 8 eV. The amount of sp3 hybridizised C atoms has been estimated by integration over the * and * band ranges in the core loss spectra. 相似文献
3.
Effective masses of conduction electrons in the sodium tungsten bronzes have been determined from the frequency of surface plasmon features in high-resolution electron energy loss spectra. Good agreement is found with effective masses from optical experiments. The results support the view that there is no major depletion in the carrier concentration at the surface of the bronzes. 相似文献
4.
The vibrational spectrum of carbon monoxide chemisorbed on Ni(110) at 300K has been recorded as a function of surface coverage. At low and intermediate coverage the adsorbate is bonded either to single nickel atoms (linear site) or to two nickel atoms in contact (B2 site). As the coverage approaches unity the spectrum changes rapidly until at saturation virtually all adsorbed molecules are of B2 type. 相似文献
5.
V. A. Sobyanin 《Reaction Kinetics and Catalysis Letters》1986,32(2):287-292
The adsorption and dissociation of nitric oxide on the Pt(100) surface have been studied using Electron Energy Loss Spectroscopy.
Pt(100).相似文献
6.
Koyama Y Mizoguchi T Ikeno H Tanaka I 《The journal of physical chemistry. B》2005,109(21):10749-10755
The electronic structures of NiO, LiNiO2, and NiO2 are studied by the electron energy loss spectroscopy at Ni L(2,3), Ni M(2,3), and O K edges. The Ni L(2,3) edge spectra suggest that the formal charge of nickel is +2 in NiO, +3 with a low-spin state in LiNiO2, and +4 with a low-spin state in NiO2. This is well confirmed by first-principles calculations. The Ni M(2,3) edge spectra show similar chemical shifts to those of the Ni L(2,3) edge. Superposition of the Li K edge spectrum, however, hinders further analysis. Although the formal charge of oxygen is -2 in all the three phases, the O K edge spectra indicate a more remarkable difference in the electronic structure of the oxygen in NiO2 than that in either NiO or LiNiO2. The spectra suggest that lithium extraction from LiNiO2 reinforces the covalent bonding between the oxygen and nickel atoms and causes a notable reduction in electron density at the oxygen atoms. 相似文献
7.
Temperature progammed electron energy loss spectroscopy: Kinetics of CH3 OH decomposition on Ni(110)
A new time-resolved electron energy loss spectrometer has been used to perform temperature programmed reaction studies the decomposition of methanol on 相似文献
8.
《Chemical physics letters》1985,118(5):478-480
By means of high-resolution electron energy loss spectroscopy the surface intermedaites formed during the interaction of methane and chemisorbed oxygen on Ni(100) were examined. For oxygen adlayers of less than monolayer, as monitored by LEED, the formation of a surface species with an EELS vibration of 1725 cm-1 was observed at 200 K. Assignment of this frequency to a surface intermediate is discussed. 相似文献
9.
Jacek Jasinski Kent E Pinkerton I M Kennedy Valerie J Leppert 《Microscopy and microanalysis》2006,12(5):424-431
The oxidation state of iron oxide nanoparticles co-generated with soot during a combustion process was studied using electron energy-loss spectroscopy (EELS). Spatially resolved EELS spectra in the scanning transmission electron microscopy mode were collected to detect changes in the oxidation state between the cores and surfaces of the particles. Quantification of the intensity ratio of the white lines of the iron L-ionization edge was used to measure the iron oxidation state. Quantitative results obtained from Pearson's method, which can be directly compared with the literature data, indicated that the L3 /L2-intensity ratio for these particles changes from 5.5 +/- 0.3 in the particles' cores to 4.4 +/- 0.3 at their surfaces. This change can be directly related to the reduction of the iron oxidation state at the surface of the particles. Experimental results indicate that the cores of the particles are composed of gamma-Fe2O3, which seems to be reduced to FeO at their surfaces. These results were also supported by the fine structure of the oxygen K-edge and by the significant chemical shift of the iron L-edge. 相似文献
10.
Bo Da Lihao Yang Jiangwei Liu Yonggang Li Shifeng Mao Zejun Ding 《Surface and interface analysis : SIA》2020,52(11):742-754
Reflection electron energy loss spectroscopy (REELS) has been used to study the optical and electronic properties of semi-infinite solid samples, aided by a theoretical model of the interaction between electrons and a solid. However, REELS has not been used to its full capacity in studying nanomaterial samples because of the difficulty in modeling the electron interaction with a layered nanostructure. In this study, we present a numerical calculation result on the spatially varying inelastic mean free path for a sample comprising an Fe layer of varying thickness on an Si substrate. Furthermore, a Monte Carlo model for electron interaction with this Fe-Si layered structure sample is built based on this inelastic scattering cross section and used to reproduce the REELS spectra of Fe-Si layered structures. The simulated spectra of the sample with varying Fe layer thickness on top of a Si substrate were compared with the experimental spectra. This comparison clearly identifies that the Fe layer remaining on top of the experimental Si substrate after Ar+ beam sputtering is in the form of a homogeneous mixed layer, where the Fe/Si interface excitation is absent in the experimental spectra owing to pulverization of the Fe/Si interface during the Ar+ sputtering process. 相似文献
11.
Electron energy loss spectroscopy (EELS), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy have been used to study iron catalysts for Fischer-Tropsch synthesis. When silica-containing iron oxide precursors are activated in flowing CO, the iron phase segregates into iron carbide crystallites, leaving behind some unreduced iron oxide in an amorphous state coexisting with the silica binder. The iron carbide crystallites are found covered by characteristic amorphous carbonaceous surface layers. These amorphous species are difficult to analyze by traditional catalyst characterization techniques, which lack spatial resolution. Even a surface-sensitive technique such as XPS shows only broad carbon or iron peaks in these catalysts. As we show in this work, EELS allows us to distinguish three different carbonaceous species: reactive amorphous carbon, graphitic carbon, and carbidic carbon in the bulk of the iron carbide particles. The carbidic carbon K edge shows an intense "pi*" peak with an edge shift of about 1 eV to higher energy loss compared to that of the pi* of amorphous carbon film or graphitic carbon. EELS analysis of the oxygen K edge allows us to distinguish the amorphous unreduced iron phase from the silica binder, indicating these are two separate phases. These results shed light onto the complex phase transformations that accompany the activation of iron catalysts for Fischer-Tropsch synthesis. 相似文献
12.
V. Oleshko V. Volkov R. Gijbels W. Jacob M. Vargaftik I. Moiseev G. Van Tendeloo 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1995,34(4):283-291
Combined structural and chemical characterization of cationic polynuclear palladium coordination compounds Pd561L60(OAc)180, where L=1,10-phenantroline or 2,2-bipyridine has been carried out by high-resolution electron microscopy (HREM) and analytical electron microscopy methods including electron energy-loss spectroscopy (EELS), zero-loss electron spectroscopic imaging, and energy-dispersive X-ray spectroscopy (EDX). The cell structure of the cluster matter with almost completely uniform metal core size distributions centered around 2.3 ±0.5 nm was observed. Zero-loss energy filtering allowed to improve the image contrast and resolution. HREM images showed that most of the palladium clusters had a cubo-octahedral shape. Some of them had a distorted icosahedron structure exhibiting multiple twinning. The selected-area electron diffraction patterns confirmed the face centered cubic structure with lattice parameter close to that of metallic palladium. The energy-loss spectra of the populations of clusters contained several bands, which could be assigned to the delayed Pd M4, 5-edge at 362 eV, the Pd M3-edge at 533 eV and the Pd M2-edge at 561 eV, the NK-edge at about 400 eV, the O K-edge at 532 eV overlapping with the Pd M3-edge and the carbon C K-edge at 284 eV. Background subtraction was applied to reveal the exact positions and fine structure of low intensity elemental peaks. EELS evaluations have been confirmed by EDX. The recorded series of the Pd M-edges and the N K-edge in the spectra of the giant palladium clusters obviously were related to Pd-Pd- and Pd-ligand bonding.V. Oleshko is on leave from the N.N. Semenov Institute of Chemical Physics of the Russian Academy of Sciences, 117421 Moscow, Russia 相似文献
13.
CH Patterson 《The Journal of chemical physics》2012,137(9):094701
Surface phonons, conductivities, and loss functions are calculated for reconstructed (2×1), p(2×2) and c(4×2) clean Si(001) surfaces, and (2×1) H and D covered Si(001) surfaces. Surface conductivities perpendicular to the surface are significantly smaller than conductivities parallel to the surface. The surface loss function is compared to high resolution electron energy loss measurements. There is good agreement between calculated loss functions and experiment for H and D covered surfaces. However, agreement between experimental data from different groups and between theory and experiment is poor for clean Si(001) surfaces. Formalisms for calculating electron energy loss spectra are reviewed and the mechanism of electron energy losses to surface vibrations is discussed. 相似文献
14.
《International Journal for Radiation Physics and Chemistry》1976,8(1-2):113-150
The experimental arrangements used by the authors for the study of optical vacuum ultra-violet and electron energy loss spectra of organic compounds are described and some theoretical aspects of studies of higher excited states are considered. Results for alkanes, benzene, naphthalene, anthracene and some more complex hydrocarbons are reviewed. Recent results obtained by reflection and electron energy loss spectroscopy for single crystals of anthracene are included and their relevance for gas phase work as well as for the understanding of exciton effects in organic solids is described. 相似文献
15.
Two coexisting adsorption states of molecularly adsorbed acetylene on the Si(001)-(2 x 1) surface have been identified by a combined study based on the high-resolution electron energy loss spectroscopy and density functional computations. Seven possible adsorbate-substrate structures are considered theoretically including their full vibrational analysis. Based on a significantly enhanced experimental resolution, the assignment of 15 C2H2- and C2D2-derived vibrational modes identifies a dominant di-sigma bonded molecule adsorbed on top of a single Si-Si dimer. Additionally there is clear evidence for a second minority species which is di-sigma bonded between two Si-Si dimers within the same dimer row (end-bridge geometry). The possible symmetries of the adsorbate complexes are discussed based on the specular and off-specular vibrational measurements. They suggest lower than ideal C(2v) and C(s) symmetries for on-top and end-bridge species, respectively. At low coverages the symmetry reductions might be lifted. 相似文献
16.
《Spectrochimica Acta Part B: Atomic Spectroscopy》1995,50(10):1281-1292
Polydisperse standard aerosols of NaCl, (NH4)2SO4 and KNO3 have been generated from their solutions by pneumatic nebulization. These aerosol particles are electron beam sensitive and therefore special precautions are necessary. A methodology is proposed for serially recording electron energy loss spectra (EELS) from sub-micrometer salt particles. The results of quantification are compared with those obtained by parallel electron energy loss spectroscopy (PEELS).Experimental conditions such as the intensity of the primary beam, time of radiation and temperature are responsible for large deviations from the theoretical values. These deviations arise because heavy mass losses occur, especially during the serial spectrum acquisition. The more time consuming serial EELS is therefore at a disadvantage relative to the parallel method.The best results are obtained for NaCl because the halogen loss can be reduced more efficiently than nitrogen and oxygen losses. The results show that nitrogen loss occurs within the first few seconds of the experiment at normal radiation doses. Even at cryogenic temperatures, losses of volatile elements cannot be avoided. 相似文献
17.
The binding energy spectrum of carbon disulphide (CS(2)) in the energy range of 9-23 eV has been measured by a high-resolution (e,2e) spectrometer employing asymmetric noncoplanar kinematics at an impact energy of 2500 eV plus the binding energy. Taking the advantage of the high energy resolution of 0.54 eV, four main peaks and five satellites in the outer-valence region are resolved. The assignments and pole strengths for these satellite states are achieved by comparing the experimental electron momentum profiles with the corresponding theoretical ones calculated using Hartree-Fock and density functional theory methods. The results are also compared in detail with the recent SAC-CI general-R calculations. General agreement is satisfactory, while the present experiment suggests cooperative contributions from (2)Π(u), (2)Σ(g)(+) states to satellite 2 and (2)Σ(g)(+), (2)Π(g) states to satellite 3. Besides, relatively low pole strength for X (2)Π(g) state is obtained which contradicts all the theoretical calculations [2ph-TDA, ADC(3), SAC-CI general-R, ADC(4)] so far. 相似文献
18.
19.
Optical gap measurements on individual boron nitride nanotubes by electron energy loss spectroscopy.
Raul Arenal Odile Stéphan Mathieu Kociak Dario Taverna Annick Loiseau Christian Colliex 《Microscopy and microanalysis》2008,14(3):274-282
Electromagnetic response of individual boron nitride nanotubes (BNNTs) has been studied by spatially resolved electron energy loss spectroscopy (EELS). We demonstrate how dedicated EELS methods using subnanometer electron probes permit the analysis of local dielectric properties of a material on a nanometer scale. The continuum dielectric model has been used to analyze the low-loss EEL spectra recorded from these tubes. Using this model, we demonstrate the weak influence of the out-of-plane contribution to the dielectric response of BNNTs. The optical gap, which can be deduced from the measurements, is found to be equal to 5.8 +/- 0.2 eV, which is close to that of the hexagonal boron nitride. This value is found to be independent of the nanotubes configuration (diameter, helicity, number of walls, and interaction between the different walls). 相似文献
20.
《Chemical physics》1987,111(3):467-479
The S 1s photoabsorption spectrum of SF4 recorded with synchrotron radiation is reported along with the electron energy loss spectrum of SF4 in the regions of S 2p, S 2s and F 1s excitation recorded under dipole dominated conditions. The electron energy loss spectrum of SF4 in the region of valence electron excitation is also reported. All of these spectra are interpreted in terms of a common manifold of upper levels which includes valence levels whose term values reflect the different axial and equatorial SF bond lengths in this molecule. The spectra are good examples of the effects of potential barriers on electronic excitation spectra. 相似文献