Spectroscopic study of plasmons in ion-irradiated single-walled carbon nanotubes

The electronic structure of single-walled carbon nanotubes was experimentally investigated using x-ray photoelectron spectroscopy, reflection electron energy-loss spectroscopy, and Auger electron spectroscopy. A shake-up satellite structure observed near the C 1s core-level lines in the x-ray photoelectron spectra at high binding energies in the range 284–330 eV due to excitation of π and π + σ plasmons was studied. The effect of irradiation by 1-keV argon ions on the shape of the spectra was analyzed. The shape of the C 1s satellite spectra was found to be sensitive to Ar⁺ irradiation in the electron energy loss range 10–40 eV corresponding to excitation of π + σ plasmons. Auger spectroscopy revealed the presence of argon on the surface of ion-irradiated samples. The argon content increased to ～4 at. % with increasing irradiation dose. An analysis of the results obtained and their comparison with the data available in the literature led to a qualitative conclusion that the bond angles of the carbon atoms making up the walls of single-walled carbon nanotubes are distorted at sites exposed to Ar⁺ irradiation.     

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.     

Correlation effects in 3d transition metals: Presence of a two-hole core-satellite in cobalt

Photoemission spectra of the 2p-level have been recorded from evaporated films of the 3d transition metals vanadium, chromium and cobalt. Structures on the high binding energy side of the spectra are observed; cobalt shows a weak satellite structure that resembles the well-known shakeup satellite in the nickel core level spectrum, only less intense, whereas the core level spectra of V and Cr only show satellites due to collective electron excitations.     

Is ionization adiabatic near threshold?

Time-dependent perturbation theory is applied to a two-level model of neon to predict the energy dependence of 2p → 3p shakeup accompanying ionization. In this picture, the outgoing electron is treated as a classical particle moving in the potential of the nucleus and the other electrons. The time dependence of the perturbation is calculated numerically and integrated to give the shakeup probability. For core ionization this model predicts the probability for shakeup at the shakeup threshold to be about 79% of the value at the sudden limit. For 2p ionization the corresponding ratio is 67%. Thus, even at the threshold the process is closer to the sudden limit than to the adiabatic limit. Experimental results are in agreement with these theoretical predictions.     

Multicomponent structure in x-ray photoelectron spectroscopy of transition metal compounds

This paper is a summary of work in progress on a comprehensive study of the nature of satellite lines in x-ray photoelectron spectroscopy. The work can be broken down into three principal areas: (1) The satellite structure arising from photoionization in the K shell of transition metal compounds has been measured using CuKα x rays. From these data the relative importance of electron shake up and multiples splitting has been ascertained. (2) A systematic study of the satellite structure following photoionization in the 2p subshell of the metal ion for first row transition metal halides, hexacyano complexes, acetyl acetonates and other miscellaneous compounds. The data can be explained in terms of monopole excitation involving either charge exchange between ligand and metal orbitals or excitation of electrons in the 3d orbital. (3) A study of multiplet splitting in the 3s subshell of nickel for a series of NiFe_xCr _2-xO₄ alloys has been carried out and compared with measurements on the hyper field interactions from Mössbauer experiments.     

Photoemission from laser excited semiconductors: Dynamic response of the electronic structure in Si

Using angle-resolved photoemission in coincidence with a pulsed Nd:Yag laser beam (hν_L = 2.33 eV), we have studied the dynamic rearrangement of the electronic states in Si in the presence of a large number of electron hole pairs created by laser photon excitation. We observed considerable changes in the valence band structure, a renormalization of the bandgap, and a satellite peak in the 2p core level emission due to more effective core hole screening.     

Shakeup spectra and core ionization potentials for formaldehyde. The role of electron spin in shakeup

The carbon and oxygen 1s ionization potentials in gaseous formaldehyde are 294.47 (6) and 539.44 (6) eV, respectively. A single shakeup peak is fou     

Inner shell excitation of CH 3F,CH 3Cl,CH 3Br and CH 3I by 2.5 keV electron impact

Small angle inelastic scattering of 2.5 keV electrons was used to study inner shell excitation in the methyl halides at energy transfers between 50 and 700 eV. Discrete peaks due to the excitation of carbon K, fluorine K, chlorine L, bromine M_{4, 5} and iodine N _{4, 5} electrons were observed. Correlations through the methyl halide series were used to aid in the assignment of features in the carbon K-shell spectra. A comparison of halogen inner-shell excitation structures with the carbon K-shell excitation structure in the same molecule allowed a complete assignment of all spectral features. The assignments proposed involve promotions of inner shell electrons to unoccupied valence and Rydberg orbitals. On the basis of our assignments of the chlorine L- and carbon K-shell electron energy loss spectra of CH ₃Cl we propose an alternate assignment of the previously reported CH ₃Cl chlorine K-shell photoabsorption spectrum.     

Electronic excitation of HgX (X = Cl,Br, I) due to electron and methyl mercury halide collisions

Electronic excitation of HgX (X = Cl, Br, I) radicals in the B-state has been observed as the result of collisions with low energy electrons and methyl mercury halide (CH₃HgX) molecules. The emission intensity has been observed to be much weaker than that observed for electron-HgX₂ collisions under similar experimental conditions. Using the strongest band head of the B-X band system, an attempt has been made to calculate the emission cross section due to electron CH₃HgX collisions at 10 eV electron kinetic energy. For HgCl, HgBr, and HgI radicals, these cross sections are 1 × 10^-18, 7 × 10^-17, and 2 × 10^-17 cm², respectively, with an estimated uncertainty of ±30%. Our measured threshold electron energy for excitation of CH₃HgX molecules and observation of the B-X emission band system and emission cross sections measured at 10 eV are greatly different from those measured by Allision and Zare [Chem. Phys. 35, 263 (1978)].     

Evidence for shakeup satellites due to surface contamination in arsenic metal and its compounds

Satellites accompanying the main peaks have been observed in the X-ray photo-electron spectra of arsenic metal and its compounds. These satellites are examined in terms of various mechanisms such as multi-electron excitation energy losses. In addition to plasm on satellites, a satellite doublet associated with the 3d peak is attributed to charge-transfer shakeup from the 2pσ level of carbon (present as a surface contamination) to the Fermi level of arsenic. Such charge-transfer shake-up satellites may be caused by a difference in the relaxation energy of surface arsenic atoms as compared to bulk arsenic atoms resulting from the presence of weakly bonded carbon.     

Optische Messung der Elektronenstoß-Anregung von Xenon und molekularem Stickstoff im Schwellenbereich mit hoher Energieauflösung

Relative optical excitation functions of Xe and N₂ have been measured in the threshold region. The inciting electron beam had a FWHM of 50 meV. The threshold behaviour of the excitation functions ofp-levels of Xenon is strongly influenced by resonances. The onset is step-like, in some cases resonance structure is to be seen just above threshold. In some excitation functions resonance structure is found immediatly above the ionization limit. This is believed to be caused by two compound states the parent states of which could be the 6d′ and the 8s′ autoionizing state of Xenon. In nitrogen, the excitation functions of two bands of the second positive group have been measured (3371 and 3755 Å), the upper levels of which are thev=0 and thev=1 levels of theC ³Π _u state. The excitation raises linear from threshold. In the 3371 Å excitation function a resonance maximum at 11.50 eV is observed, where the cross section is increased due to resonance population by about 100%, as measured with a FWHM of 50meV of the electron beam. The broad absolute maximums of the excitation functions are found to lie at 14.0±0.1 eV in the case of the 3371 Å- and at 14.3±0.1 eV in the 3755 Å-band.     

A systematic angle-resolved photoelectron study of π orbitals in unsaturated organic molecules

The angular distribution parameter β has been determined for the π orbitals of 1,1-dichloroethylene, tetrachloroethylene, tetrafluoroethylene, propylene, 1-butene, isobutylene, cis-2-butene, trans-2-butene, 1,3-butadiene, cyclopentene, methylacetylene and furan in the photon energy range 10–30 eV using dispersed polarized synchrotron radiation. The energy dependence of β in the photoelectron energy range 2–10 eV was found to be similar for all the π orbitais investigated. The potential use of the energy dependence of β as an aid in making molecular-orbital assignments is discussed. Resonance photoionization features similar to those observed for the π orbitals of acetylene, ethylene and benzene were found in many of the π orbitals of the molecules investigated herein. Possible explanations for these resonance features are discussed.     

Vibrational analysis of the Raman spectra of polycrystalline cis-2-butene

The vibrational assignments and potential energy distributions for cis-2-butene were examined by transferring appropriate force constants from trans-2-butene and the model systems, cis-1,2- and trans-1,2-difluoroethylene. The model fluoroethylene systems provided both the crucial interaction force constants, which account for effects across the double bond in cis-2-butene, and the skeletal out-of-plane force constants. The zero-order frequencies calculated for cis-2-butene from the transferred potential function agreed quite well with the low temperature Raman spectra of the polycrystalline material.     

Excitation of lowest electronic states of the uracil molecule by slow electrons

The excitation of lowest electronic states of the uracil molecule in the gas phase has been studied by electron energy loss spectroscopy. Along with excitation of lowest singlet states, excitation of two lowest triplet states at 3.75 and 4.76 eV (±0.05 eV) and vibrational excitation of the molecule in two resonant ranges (1?C2 and 3?C4 eV) have been observed for the first time. The peak of the excitation band related to the lowest singlet state (5.50 eV) is found to be blueshifted by 0.4 eV in comparison with the optical absorption spectroscopy data. The threshold excitation spectra have been measured for the first time, with detection of electrons inelastically scattered by an angle of 180°. These spectra exhibit clear separation of the 5.50-eV-wide band into two bands, which are due to the excitation of the triplet 1³ A?? and singlet 1¹ A?? states.     

Many-body effects in l2mm auger electron spectra of Ge(CH3)4 excited by Mg Kα X-rays

The Ge:L₂MM Auger electron spectra excited by Mg Kα X-rays from Ge(CH₃)₄ free molecules have been compared with the corresponding spectra excited by Al Kα X-rays. The Al Kα excited spectra have characteristic features of the diagram Auger transitions, because the excitation energy is far above the L₂ ionization threshold. The energy of Mg Kα photons is 1.21 eV below the Ge:L₂ ionization threshold and thus the Mg Kα excited L₂MM Auger electron spectra indicate many-body effects, post collision interaction (PCI) effects and spectator Auger satellite structures. The L₂M_4,5M_4,5 type spectrum displays both these features but the L₂M_2,3M_4,5 type spectrum has only a spectator Auger satellite structure, because the (3p⁻¹3d⁻¹nl) final state interferes with the (3s) hole state.     

Infrared spectroscopic studies of the rare gas atom perturbed S1(0) rovibron band of solid parahydrogen

We report high resolution infrared absorption studies of rare gas (Rg) atom doped solid parahydrogen in the hydrogen S₁(0) region around 4486 cm⁻¹. At low Rg atom concentrations (∼0.1%), satellite transitions appear in the S₁(0) region due to rovibrational excitation of parahydrogen molecules with one nearest-neighbor Rg atom. The Ne satellite feature differs qualitatively from the Ar, Kr, and Xe satellite features for reasons described within. The frequency of the S₁(0) satellite features linearly shift to lower energy as the polarizability of the Rg atom increases while the absorption coefficients increase with the square of the Rg atom polarizability. Rotational calculations are performed for H₂ with a nearest-neighbor Rg atom assuming a rigid hexagonal close-packed lattice structure. The calculated fine structure of the S₁(0) satellite features agree qualitatively with lifting of the 2J+1 degeneracy of the v = 1, J = 2 upper state caused by the anisotropy in the Rg-H₂ intermolecular potential. The discrepancy between the calculated and measured Rg atom S₁(0) satellite features may signal partial delocalization of the J = 2 roton onto neighboring parahydrogen molecules.     

Inner-shell excitation and EXAFS-type phenomena in the chloromethanes

Small angle inelastic scattering of 2.5 keV electrons was used to study the inner-shell excitation of CH₄, CH₃Cl, CH₂Cl₂, CHCl₃, CCl₄ and C₂H₅Cl in the regions of carbon 1s, chlorine 2p and chlorine 2s excitation. Structure observed below the carbon 1s ionization threshold in each molecule is assigned to promotions of a carbon 1s electron to unoccupied valence and Rydberg orbitals. Trends in the distribution of spectral intensities through the series of chloromethane carbon 1s spectra are discussed in terms of the growth of a potential barrier. Broad features are observed in the chlorine 2p continua of CH₂Cl₂, CHCl₃ and CCl₄ and the carbon 1s continuum of CCl₄ which are assigned as the energy loss equivalent of extended X-ray absorption fine structure (EXAFS).     

K X-ray satellite transitions in cobalt

Bombardment of cobalt with 42 MeV oxygen ions is seen to produce multiple inner shell electron excitation.Kα andKβ X-rays are measured and compared to Hartree-Fock-Slater calculated energies. This study of cobalt is the highestZ element where the satellite X-ray spectrum has been studied with good resolution.     

Effect of relaxation and decay of a charge transfer shakeup satellite on Auger-electron spectroscopy spectra and Auger-photoelectron coincidence spectroscopy spectra of adsorbates

An electron excited to an unoccupied part of adsorbate–substrate hybrid states in a chemisorbed molecule by a resonant core electron excitation or charge transfer (CT) shakeup may delocalize on time scale of core-hole decay so that the excited core-hole state relaxes partly or completely to a fully relaxed one. The Auger decay of the fully relaxed core-hole state via the relaxation of the excited one introduces an additional feature in the resonant Auger-electron spectroscopy (RAES) spectrum and the AES spectrum. However, the additional feature in the RAES spectrum is a normal AES spectrum by decay of the fully relaxed core-hole state, whereas the one in the AES spectrum is the AES spectrum by decay of the fully relaxed core-hole state broadened by the photoelectron spectroscopy (PES) CT shakeup satellite weighted by the branching ratio of the relaxation width. The discrepancies between the AES spectrum measured at high above the ionization threshold and the additional feature in the RAES spectrum consist of the symmetric-like part by the decay of the fully relaxed core-hole state via the relaxation of the CT shakeup state and the asymmetric part by the direct decay of the shakeup states. The asymmetric part increases with a decrease in the hybridization strength. This explains the variation with the hybridization strength in the discrepancies between the RAES spectra and the AES spectra of chemisorbed molecules such as CO/Ni, CO/Cu and CO/Ag. A comparison of the singles PES spectrum with the one measured in coincidence with the AES main line of a selected kinetic energy (KE) provides the delocalization rate of the excited electron in the CT shakeup state as a function of photoelectron KE. The coincidence measurement to obtain the partial singles PES spectrum is discussed.     

Resonances at collisions of slow electrons with cadmium atoms and ions

Using the crossed-beam method and a hypocycloidal electron spectrometer, the energy dependence of the ionization cross section for the cadmium atom has been studied in the near-threshold region and the elastic scattering of slow electrons at an angle close to 180° by Cd⁺ ions was studied for the first time. Within the region under study (0–7 eV above the first atomic ionization potential), a resonance structure determined by the contribution of atomic autoionization states is revealed in both the ionization curve and differential cross section of elastic scattering. The structure in the measured curves has been analyzed with the use of data on the ejected-electron spectra obtained under the excitation of autoionization states of Cd atoms, as well as the data on the optical excitation functions for the atomic spectral lines at λ=430.7 nm (5¹ P ₁-8¹ S ₀), 515.5 nm (5¹ P ₁-7¹ S ₀), 298.0 nm (5³ P ₂-6³ D _j ), and 361.0 nm (5³ P ₂-5³ D _j ).