Electron energy-loss spectroscopy of UHV-cleaved NiO (100) surfaces

Electron energy-loss spectroscopy of ～ 200 eV electrons has been applied to the study of the electronic states of clean NiO (100) surfaces. Initial attempt has been made on the identification of observed peaks, and they are attributed to the one-electronic transitions (O^2-2p → Ni²⁺3d, 4s and 4p; Ni²⁺3d → 4p, 3p → 3d and 4s), and the collective excitations (bulk plasmons of O^2-2p, Ni²⁺3d electrons, and coupled 2p and 3d electrons).     

Electron energy loss spectroscopy and ultraviolet photoemission of TmSe

Intraionic Tm²⁺ and Tm³⁺ ? → d and p → d charge transfer transitions are identified in the energy loss spectra of 100eV electrons of TmSe by comparison with X-ray photoemission data. In contrast the ultraviolet photoemission spectra with photon energies up to 21.2 eV do not show any evidence for the intermediate valence character of TmSe due to matrix element effects.     

Electron energy-loss spectra of clean and hydrogen-covered Cr(110) surfaces

Electron energy-loss spectra of clean and hydrogen-covered Cr(110) surfaces have been investigated in the spectral range of 0–80 eV for primary energies of 60–500 eV. The observed peaks for the clean surface are at the loss energies of 2, 3.5, 5.5, 9.6, 23, 35, 42, 48 and 55 eV. The 3p-excitation spectra for high primary energies (> 250 eV) are in good agreement with the corresponding optical spectrum. The edge at & 42 eV observed for low primary energies is tentatively attributed to the onset of the transition from the 3p subshell to the local 4s-band in the vicinity of the core hole. A characteristic energy-loss at ≈ 15.5 eV is observed after hydrogen adsorption. The 3p-spectrum is not influenced by hydrogen adsorption, indicating that the excitation is of a localized character.     

Pressure dependent optical absorption edge shift and compressibility of CdCr2Se4 single crystals

The pressure shift of the optical absorption edge (dE_g/dp = (1.1 ± 0.1) × 10^?6 eV bar^?1) and the compressibility (κ = (1.3 ± 0.) × 10^?6 bar^?1) of single crystalline CdCr₂Se₄ have been measured at ambient temperature. These data suggest an interpretation of the fundamental absorption in terms of either p → p interband or p → localized d charge transfer transitions, but exclude excitations involving s-band states.     

The electron energy loss spectrum of Br on Au (100)

The electron energy loss spectrum of Br on Au (100) shows a sharp loss at 2.5 eV accompanied by a weaker broader feature at 5.5 eV and a broad enhancement centred at 16 eV. It is suggested that an adsorbate resonance lies above the top of the d-band allowing adsorbate → free metal state transitions without appreciable coupling to or competition from metal excitations.     

3s- and 3p-core level excitations in 3d-transition metal oxides from electron-energy-loss spectroscopy

3s- and 3p-core level excitations for a large number of 3d-transition metal oxides, with a formal 3d occupation from 3d⁰ to 3d¹⁰, have been measured by electron energy loss spectroscopy in reflection geometry (REELS) with primary energies 200 eV≤E ₀≤1600 eV. Their intensities decrease systematically with the formal 3d-count, classifying them as transitions to empty 3d-states. The structure of the 3s excitations is analysed in detail and is compared to the 3s-XPS photoemission spectra of the samples. This 3s-REELS structure and its change with the 3d occupation can be explained by the assumption that the excitation arises mainly from a 3s²3dⁿ→3s¹3dⁿ⁺¹ quadrupole transition.     

Electron energy-loss spectra of clean and gas-covered Ni(100) surfaces

Electron energy-loss spectra have been measured on Ni(100) surfaces, clean and following oxygen and carbon monoxide adsorption, at primary energies of 40–300 eV. The observed peaks at 9.1, 14 and 19 eV in the clean-surface spectrum are ascribed to the bulk plasmon of the 4s electrons, the surface plasmon, and the bulk plasmon of the coupled 3d + 4s electron, respectively, and the weak but sharp peak at 33 eV is tentatively attributed to the localized many-body effect in the final state. Assignments of the loss structures on the gas-covered surfaces have been attempted.     

Fundamental absorption spectra of transition metal chlorides

The optical absorption spectra of MnCl₂, FeCl₂, CoCl₂, and NiCl₂ have been measured over the energy range from 2 to 30 eV. The gross features of the spectra, especially broad bands above 10eV, are alike in all of the four materials. The charge transfer bands due to the electronic transitions from the 3p level of chlorine to the 3d and 4s levels of metal ions and the band due to the 3d → 4s transition are assigned in the spectra.     

Charge-transfer transitions and optical spectra of chromites

Specific features of charge-transfer states and charge-transfer transitions of the O_2p → Cr_3d type in octahedral complexes (CrO₆)^9? have been considered in the cluster approximation. Reduced matrix elements of the electric-dipole moment operator on many-electron wave functions, which are the initial and final states for charge-transfer transitions, are calculated. The results are parameterized, and the relative intensities of different allowed charge-transfer transitions in the absence of mixing of different charge-transfer configurations with identical symmetry are calculated. This mixing is taken into account within the Tanabe-Sugano theory, and the true energies and intensities of many-electron charge-transfer transitions are obtained. The Coulomb interaction between 2p electrons of O^2? ligands and 3d electrons of the central Cr³⁺ ion in (CrO₆)^9? cluster is considered. The influence of this interaction on the optical spectra is found to be insignificant. Simulation of the optical spectra of chromium oxides has shown the presence of a band of complex charge-transfer transitions composed of 33 lines with a total width of about 8 eV. The model spectrum is in adequate agreement with the experimental data, which indicates limited applicability of the widespread view that charge-transfer transition spectra have a simple structure.     

The adsorption of CO on Cu surfaces studied by electron energy loss spectroscopy

Electron energy loss spectroscopy (ELS) in the energy range of electronic transitions (primary energy 30 < E₀ < 50 eV, resolution ΔE ≈ 0.3 eV) has been used to study the adsorption of CO on polycrystalline surfaces and on the low index faces (100), (110), (111) of Cu at 80 K. Also LEED patterns were investigated and thermal desorption was analyzed by means of the temperature dependence of three losses near 9, 12 and 14 eV characteristic for adsorbed CO. The 12 and 14 eV losses occur on all Cu surfaces in the whole coverage range; they are interpreted in terms of intramolecular transitions of the CO. The 9 eV loss is sensitive to the crystallographic type of Cu surface and to the coverage with CO. The interpretation in terms of d(Cu) → 2π¹(CO) charge transfer transitions allows conclusions concerning the adsorption site geometry. The ELS results are consistent with information obtained from LEED. On the (100) surface CO adsorption enhances the intensity of a bulk electronic transition near 4 eV at E₀ < 50 eV. This effect is interpreted within the framework of dielectric theory for surface scattering on the basis of the Cu electron energy band scheme.     

Dielectric function of YBa2Cu3O7-δ between 50 meV and 50 eV

Electronic excitations with polarization parallel to the CuO₂-planes in single-crystalline YBa₂Cu₃O₇ and YBa₂Cu₃O₆ have been investigated by optical reflectance and by highenergy electron energy-loss spectroscopy in transmission in the energy ranges from 50 meV to 6 eV and 0.2 eV to 150 eV, respectively. From a combination of these experimental data the dielectric function, the reflectivity and the optical conductivity have been obtained in a wide energy range. The observed spectra are interpreted in terms of optical phonons, free-carrier absorption, transitions across the charge-transfer gap, further interband transitions, low-lying core-level excitations, excitonic transitions and valence conservingd-d transitions within the Cu 3d shell combined with O 2p intraband transitions. The charge carrier plasmon and the 4 eV-excitation in YBa₂Cu₃O₆ show quadratic dispersions in momentum transfer. From the dispersion constant of the plasmon a mean value of the Fermi velocity of the charge carriers parallel to the CuO₂ planes has been derived.     

Nonlinear optical spectroscopy of electronic transitions in hexagonal manganites

The hexagonal rare-earth manganites RMnO₃ (R = Sc, Y, Ho, Er, Tm, Yb, Lu) are a group of materials with an unusual combination of magnetic, electric and optical properties. The electronic structure of these materials was studied by second harmonic (SH) spectroscopy in the range from 1.2 to 3.0 eV. Faraday rotation and absorption spectra were measured in the range from 1.0 to 1.6 eV. Broad bands at ∼1.7 eV and ∼2.7 eV are assigned to electronic transitions between Mn³⁺(3d⁴) levels. The SH spectra are discussed on the basis of a recently developed microscopic theory. Received: 26 April 2001 / Published online: 18 July 2001     

Electronic excitations on clean and adsorbate covered Pd(111) by angle resolved electron energy loss spectroscopy

Electronic excitations on clean and adsorbate covered Pd(111) have been investigated by angle resolved electron energy loss spectroscopy. Primary energies in the range of 50–1000 eV were chosen for strong specular reflection to emphasize elastic diffraction-before-loss processes. The clean Pd spectra are compared with optical data, and good correspondence is found for the optical limit (q ? 0). The loss features are interpreted in terms of plasmon resonances and interband transitions within the framework of a recent band structure calculation. Virtually no dispersion is observed for the intrinsic Pd losses, but vertical interband transitions decay fast in the dispersive (q ≠ 0) spectra. Two adsorbate systems are investigated in this study: CO in a disordered adsorbate layer and bromine in a well-ordered $\text{(}\text{3×}\text{3 )R30°}$ structure. Adsorbate derived loss features are generally prominent in the nonspecular (q ≠ 0) spectra. While no dispersion is seen for the intramolecular 13.5 eV excitation of adsorbed CO, dispersion up to 1 eV is found for the Br 4p derived loss feature of the ordered overlayer. This is discussed in terms of a two-dimensional adsorbate band structure of bromine.     

Inner shell excitation,valence excitation and core ionization in NF3 studied by electron energy-loss and X-ray photoelectron spectroscopies

Electron energy-loss Spectroscopy (EELS) at impact energies of 2.5–3 keV has been used to obtain the electron excitation spectra for the N 1s (K-shell), F 1s (K-shell) and valence shell regions of NF₃. The inner shell spectra were recorded using small angle scattering (?1° ) while the valence shell spectrum was obtained at zero degree scattering angle. The inner shell excitation spectra show a strongly enhanced 1s→ δ^* type transition and continuum features which are typical for molecules with highly electronegative ligands. One of the peaks in an earlier published photoabsorption study of the N 1s region has been shown to be due to a N₂ impurity. The valence shell electron energy-loss spectrum shows a number of transitions which are considered to be mainly due to valence-valence type transitions, with also some evidence of Rydberg structure.The X-ray photoelectron spectra (XPS) of the N 1s and F 1s electrons along with their associated satellite structures have also been recorded using Al Kα (1486.58 eV) radiation. The vertical ionization potentials for the N 1s and F 1s electrons were found to be 414.36 (10) eV and 693.24 (10) eV, respectively. Both spectra exhibit a rich and different satellite structure. These “shake-up” features in the satellite XPS spectra are compared with continuum features of the inner shell electron energy-loss spectra and also with the valence shell spectrum.     

3s- and 3p-core level excitations in 3d-transition metal oxides from electron-energy-loss spectroscopy

3s- and 3p-core level excitations for a large number of 3d-transition metal oxides, with a formal 3d occupation from 3d⁰ to 3d¹⁰, have been measured by electron energy loss spectroscopy in reflection geometry (REELS) with primary energies 200 eV≤E ₀≤1600 eV. Their intensities decrease systematically with the formal 3d-count, classifying them as transitions to empty 3d-states. The structure of the 3s excitations is analysed in detail and is compared to the 3s-XPS photoemission spectra of the samples. This 3s-REELS structure and its change with the 3d occupation can be explained by the assumption that the excitation arises mainly from a 3s²3dⁿ→3s¹3dⁿ⁺¹ quadrupole transition.     

Electron energy-loss measurements on 1,3-cyclohexadiene and 1,4-cyclohexadiene

Electron energy-loss measurements have been performed on the vapours of 1,3-cyclohexadiene and 1,4-cyclohexadiene up to 40 eV. The first valence shell excitations which have been calculated by Mulliken are identified in the spectra. Comparison with the Im (?) spectra of polycrystalline samples corroborate these assignements.     

Electron energy loss spectroscopy study of the initial stage of lanthanum oxidation

The electron energy loss spectra (EELS) of a pure metallic lanthanum surface and variations in these spectra at the initial stages of surface oxidation were studied. The measurements were performed at primary-electron beam energies E _p from 200 to 1000 eV. A very pronounced peak at a loss energy of about 7.5 eV arises due to transitions from the La4d electronic states of the valence band into the empty La4f electronic states of the conduction band at 5.0–5.5 eV above the Fermi level. Marked changes are observed in the EELS during the oxidation of lanthanum: the peak at an energy of 7.5 eV disappears, and the peak at 13.5 eV corresponding to bulk collective energy loss in lanthanum oxide becomes more pronounced. The results obtained are discussed in terms of the electronic structure of lanthanum and lanthanum oxide.     

Luminescence characteristics of the Pr3+ ion in SrAlF5

The paper reports on a study of luminescence and excitation spectra of SrAlF₅:Pr³⁺ (0.5 mol %) polycrystals performed at 10 and 300 K with synchrotron radiation in the range from 5 to 25 eV. The Pr³⁺ ions in SrAlF₅ were shown to emit successively two photons in transitions from the ¹ S ₀ and ³ P ₀ levels. The main energy characteristics of the compound, namely, the position of the 4f → 5d excitation band (5.95–8.0 eV), the energy separation between the ¹ S ₀, 4f and the lowest 5d levels (～0.15 eV), and the SrAlF₅ band gap width (～12 eV), were determined. SrAlF₅:Pr³⁺ was found to possess a number of features not found in other Pr³⁺-activated fluorides.     

Electronic structure of the valence bands of H2-, Mg- and Pt-phthalocyanine derived from soft X-ray emission and photoelectron emission spectra

The soft X-ray emission and photoelectron emission spectra of H₂-, Mg- and Pt- phthalocyanine (PC) obtained using synchrotron radiation are reported and compared. In this way, an overall view of the pattern of valence bands is obtained and the electronic structure determined in terms of the component partial densities of states. In particular, from the valence p → 1s carbon and nitrogen K-emission spectra we determine for all three compounds the C and N 2p-like valence-band density of states with strong maxima located at binding energies of 8, 11 and 13.5 eV (carbon 2p) and 8 eV (nitrogen 2p) below the vacuum level. For PtPC the partial density of d-like valence states is determined from photoelectron emission difference-spectra and compared to previous XPS results. The sharp (1.2 eV FWHM) maximum of the Pt-derived partial density of states, observed at 6.9 eV binding energy, is assigned to the ⁴F term of a 5d⁸6s final-state configuration. A second, broader maximum at around 9.5 eV binding energy contains contributions from other terms of this 5d⁸ configuration, as well as from a 5d⁷ satellite (shake-up multiplet).