Excitation of inner-shell states of CO2, COS,CS2, N2O and C2H2 by low energy electron impact

The design of an electron impact spectrometer for use in the study of inner-shell electric-dipole-forbidden transitions is described. The use of the spectrometer to investigate spin-forbidden transitions to inner-shell excited states of CO₂, COS, CS₂, N₂O and C₂H₂ is reported. For all these molecules, excitation of inner-shell triplet states has been observed.     

Photoelectron spectra of bis-cyclopentadienyl metal dihalides

He(I) and HE(II) photoelectron spectra are reported for (η-C₅H₅)₂MX₂ (M = Ti; X = F, Cl, Br, I: M = Zr, Hf; X = Cl, Br: M = Ta; X = Cl, Br) and (η-MeC₅H₄)₂MX₂ (M = Nb, X = Cl: M = Mo; X = Cl, Br, I). A substantial variation is found in the ordering of the halogen and cyclopentadienyl ionizations, the order being dependent on the metal as well as on the halogen. The compounds may be divided into three classes, namely, those in which the electrons in cyclopentadienyl e₁ orbitals ionize at a lower energy than those occupying halogen pπ orbitals, those in which halogen pπ electrons have lower ionization energy than cyclopentadienyl e₁ electrons and those in which the corresponding electrons arise from extensively delocalized molecular orbitals with significant contributions from both these categories of fragment orbital.     

K-shell excitation of CH4, NH3, H2O,CH3OH,CH3OCH3 and CH3NH2 by 2.5 keV electron impact

The regions around the respective carbon, nitrogen and oxygen K-edges of CH₄, NH₃, H₂O, CH₃OH, CH₃OCH₃ and CH₃NH₂ have been investigated by electron energy loss spectroscopy using a beam of 2.5 keV electrons. All spectra show a number of discrete peaks just below the K-shell ionization threshold. These discrete structures have been interpreted as being associated with the promotion of a K-shell electron to Rydberg orbitals which converge to the K-shell ionization threshold.     

Chemisorption and decomposition reactions of oxygen-containing organic molecules on clean Pd surfaces studied by UV photoemission

We have used uv photoeinission (primarily at a photon energy hv = 40.8 eV) to study chemisorption and decomposition reactions of small oxygen-containing organic molecules on clean polycrystalline Pd surfaces at 120 and 300 K. These molecules include methanol (CH₃OH), dimethyl ether (CH₃OCH₃) formaldehyde (H₂CO), acetaldehyde [H(CH₃)CO], and acetone [(CH₃)₂CO]. Chemisorption bonding of these molecules to the Pd surface occurs primarily through the lone-pair orbitais associated with the oxygen atoms, as evidenced by chemical bonding shifts of these orbitais toward larger electron binding energy relative to the other adsorbate valence orbitals. At 300 K all the molecules studied decompose on the surface, resulting in chemisorbed CO. Since chemisorbed (as well as condensed) phases of some of these molecules (CH₃OH and H(CH₃)CO) are observed at low temperature, the decomposition to CO is a thermally-activated reaction. The observed orbital shifts associated with chemisorption bonding are used to make rough estimates of interaction strengths and chemisorption bond energies (within the framework of Mulliken's theory of electron donor-acceptor complexes as applied to chemisorption by Grimley). The resulting heats of chemisorption are consistent with the observed surface reactions.     

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.     

Classical trajectory calculations for state-resolved Penning ionisation reactions of polycyclic aromatic hydrocarbon C10H8 in collision with He*(23S)

ABSTRACT

The reaction dynamics of Penning ionisation of a polycyclic aromatic hydrocarbon (PAH), naphthalene C₁₀H₈, in collision with the metastable He*(2³S) atom is studied by classical trajectory calculations using an approximate interaction potential energy surface between He* and the molecule, which is constructed based on ab initio calculations for the isovalent Li?+?C₁₀H₈ system. The ionisation width (rate) around the molecular surface are obtained from overlap integrals of the He 1s orbital and the molecular orbital. The calculated collision energy dependences of partial Penning ionisation cross sections (CEDPICS) in the range 50–500?meV at 300?K have reproduced the experimental results semi-quantitatively. The opacity functions, which represent the reaction probability with respect to the impact parameter b, are discussed in connection with collision energy, interaction with He* and the exterior electron density of molecular orbitals. They indicate that the collisional ionisations of C₁₀H₈ can be classified into three types: π electron ionisations with negative collision energy dependences which are predominantly determined by attractive interaction with He*; σ orbitals ionisations of the hardcore type; σ orbital ionisations which reflect interaction potentials around CH bonds. The critical impact parameters b_c become larger with increasing collision energy due to the centrifugal barrier.     

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).     

$Ab~initio$ and experimental study of the K-shell spectra of s-triazine

The carbon and nitrogen K-shell spectra of gaseous s-triazine have been studied using inner-shell electron energy loss spectroscopy (ISEELS) method. Ab initio Configuration Interaction calculations have been carried out in order to assign the observed bands. As in many similar molecules, both spectra are dominated by an intense π^* peak, followed by lower intensity features. At the C1s edge, the calculations show that some previous assignments made using an underestimated core ionisation energy of about 2.5 eV have to be revisited. At the nitrogen edge, the calculations predict a high intensity π^* doubly excited state lying below the ionisation threshold, which could be responsible for one the most intense observable bands at 405.32 eV.     

The diamond surface: III. Differential cross-sections for inelastic scattering

The differential cross-section for K-level ionisation for carbon in diamond and graphite have been derived from the Auger yield. The model is based on exponential attenuation of the outgoing Auger electrons. This model was extended to analyse the K-shell ionisation loss spectra. From the energy dependence of the loss peaks in diamond and graphite, the threshold peak k₀ has been attributed to a single high-angle back-scattering event. The peaks k₁, K₂ and K₃ can be explained in terms of a double scattering mechanism. The loss peak K₅ can be assigned to a triple scattering process.     

Effect of acids on the gamma-radiolysis of frozen aqueous systems of some organic compounds

Abstract

ESR spectra of γ-irradiated frozen aqueous solutions of a number of organic compounds such as alcohols, ether, acetone and tetrahydrofurans have been examined in the presence and absence of mineral acids such as H₂SO₄. The presence of the acid is found to cause an intensification of the organic radical ESR spectra as compared with the acid free solutions. Also, the presence of the organic compounds in frozen aqueous H₂SO₄ suppresses the formation of both H-atoms and SO₄ ^? radical ions. These results have been explained on the basis of reactions of the electrons and holes, or excitons, primarily formed by the action of radiation on the substrate ice.     

Inner shell electron energy loss spectra of the methyl amines and ammonia

Electron energy loss Spectroscopy has been used to obtain the inner shell excitation spectra of the methyl amines CH₃NH₂, (CH₃)₂NH and (CH₃)₃N for both the N 1s and C 1s regions. A spectrum of the N 1s region of NH₃ is also presented at higher resolution than previously published data. The C ls spectra are all very similar and the discrete portions may be assigned to Rydberg transitions. However, features attributable to a σ^* shape resonance are observed just above the N 1s and C ls ionization edges. The NH₃ spectrum is ascribed to Rydberg transitions. The N 1s spectra of the methyl amines, however, become increasingly dominated by a σ* resonance in the continuum with increased methylation. The features in the inner-shell spectra are compared with the reported valence-shell optical absorption spectra and support the Rydberg assignment. The inner-shell spectra of (CH₃)₃N and NH₃ are also compared with previously published inner shell electron energy loss spectra of NF₃ and the third row phosphorus analogues PF₃,P(CH₃)₃andPH₃.     

(e,2e) Spectroscopy of ethane

The 400-eV and 1200-eV non-coplanar symmetric (e, 2e) reaction has been used to measure the momentum distributions of electrons in the individual valence orbitals of ethane as well as to measure the complete separation energy spectra in the valence region. The shapes and relative magnitudes of the momentum distributions agree well with those calculated using the plane wave off-shell impulse approximation and double zeta basis molecular orbital wave functions. The ground state of C₂H₆⁺ is shown to be 1e_g^?1, with the vertical ionization potential being 12.25 ± 0.1 eV. Considerable structure due to configuration interaction is observed in the separation energy region 29–55 eV. Much of this structure can be assigned to the 2a_1g orbital.     

Geometric and electronic structures of AlnCum (n = 5–9, m = 1–3) clusters: genetic algorithm combined with ab initio models

The geometries, stabilities and electronic structures of Al _n Cu _m (n?=?5–9, m?=?1–3) clusters were explored by using the genetic algorithm combined with ab initio methods. The geometric structures are almost spherical when the valence electrons are around the magic number 20, otherwise the structures are oblate or prolate. The stabilities of the clusters are related to both the Cu/Al ratios and the electronic configurations. The clusters with lower Cu/Al ratios have high stabilities. The molecular orbitals are in accord with the shell structures predicted by the jellium model. The 3d orbitals of the Cu atoms are localised, although their orbital energies are between the 1P and 1D jellium orbitals. The Al₆Cu₂ with 20 valence electrons forms closed 1S²1P⁶1D¹⁰2S² shells, and shows large binding energy and removal energy, large ionisation potential and small electron affinity. For the no-magic clusters, the structure deformation leads to crystal-field-like splitting of the degenerate shells and stabilises the clusters.     

Molecular effects in ion-induced secondary electron spectra

The energy spectra of slow secondary electrons from a copper surface under bombardment with H⁺, H⁺₂, and H⁺₃ ions have been measured at an energy of 200 keV/atom. Distinct molecular effects are revealed in the ratios of the respective distribution curves for molecular ion and proton impact.     

Molecular orbital momentum distributions and binding energies for H2O using an electron impact coincidence spectrometer

The construction and operation of an instrument which uses the techniques of coincidence counting and electron impact spectroscopy is reported for the study of molecular ionization at large momentum transfer in which the two outgoing electrons are detected at 45° to the incident beam. Variation of the incident energy provides binding-energy spectra for Xe, CH₄ and H₂O up to 45 eV. Alternatively variation of the azimuthal angle (symmetric, non-coplanar geometry) gives a measure of the electron momentum distribution for any selected orbital in the binding-energy spectrum. Momentum distributions for the four valence orbitals of H₂O are compared with various wavefunctions from the literature.     

K-shell excitation spectra of CO,N2 and O2

Electron energy loss spectra of CO, N₂ and O₂ have been recorded in the regions of carbon, nitrogen and oxygen K-shell excitation and ionisation. These results are compared to previous energy loss, photoabsorption and theoretical studies of the same spectral regions. Several inconsistencies in the published spectra are clarified in the present work. Comparisons with recent calculations of the K-shell continua of these molecules are presented. Vibrational structure in the K → π * transitions of CO (C 1s) and N₂ (N 1s) has been resolved in high-resolution studies (< 0.1 eV FWHM) of these species.     

He(I)/He(II) photoelectron band intensity ratios for simple organic molecules

Band intensifies in the He(I) and HE(II) photoelectron spectra of some simple organic molecules (methanol, methylamine, formaldehyde, acetaldehyde, formic acid, acetic acid, methyl formate, ethylene, butadiene and methyl isothiocyanate) have been measured. The relative band intensity ratios for a number of ionizations from n and π orbitals are presented.     

Electron-Impact Fragmentographic Fluorescence Spectroscopy of Ethanol,Acetaldehyde, 1- and 2-Propanol and Acetone

Abstract

Gaseous ethanol, acetaldehyde, 1-propanol, 2-propanol and acetone at pressures of 2 × 10^?5 to 5 × 10^?4 torr were irradiated with electrons of energies 0-1000 eV. The visible-region fluorescence of the excited fragments was then measured. Studies included pressure dependence, electron energy dependence, threshold energy measurements, and excitation curve measurements. The aim of the research was to ascertain if molecules of similar structure could be differentiated by their spectra.     

Energieverluste monochromatisierter 30 keV-Lithiumionen an Argon und Äthylen

The energy loss spectra of 30-keV Li₇ ⁺ ions after interaction with argon and ethylene have been studied. Wien filters were used as monochromator and energy analyzer, an energy resolution of 0.2 eV was achieved. The ion energy loss spectra obtained differ from those taken with electrons at the same primary energy mainly in two points: In the ion spectra energy losses are found with strong intensities corresponding to optically forbidden transitions which are not excited by fast electrons. Furthermore in the energy range beyond the first ionization limit energy losses appear which are due to charge transfer into excited states of the lithium atom and re-ionization.     

Absorptionsspektrum des Ce3+-Ions und Schwingungsspektrum im CeCl3·7H2O und CeCl3·7D2O

The absorption spectra of CeCl₃·7 H₂O, LaCl₃·7 H₂O, CeCl₃·7 D₂O and LaCl₃·7 D₂O have been measured at low temperatures in the region of the 4 f→4 f infrared transitions. The energy levels of the Ce³⁺-ion in these compounds have been derived. The infrared phonon transitions have also been determined from the reflection spectra of these crystals measured in the region between 4000 cm^?1 and 50 cm^?1. Some of the energy levels of the Ce³⁺-ions in the deuterated crystals are shifted for about 10 wavenumbers against those in CeCl₃·7 H₂O. These shifts are probably due to an interaction of the electronic levels with resonant phonon-states in one or the other of the two compounds.