Assignment of photoelectro bands for naphthalene and anthracene by penning ionization electron spectroscopy

The Ne¹(³P₂) Penning electron spectra and the Ne I photoelectron spectra were measured in the gas phase. The observed systematic differences in their relative intensities were interpreted in terms of the electron distributions of the relevant molecular orbitals and used for assignment of the deep π bands, π₁ (12.4 eV) for naphthalene, and π₂ (11.9 eV) and π₁ (12.8 eV) for anthracene.     

An interpretation of the N2 photoelectron spectrum

The inner-valence (20–36 eV) photoelectron spectrum of N₂ is interpreted by comparing with various spectra (such as absorption, N⁺ yield, fluorescence-yield, and core-level photoelectron spectra). This comparative study confirms the previous assignments on the bands at 25.3 and 29.0 eV and clarifies the controversial assignments on the bands at 32.6 and 35 eV (weak). Also, this study identifies for the first time a weak but sharp band at 33.3 eV.     

Photoelectron and penning ionization electron spectroscopic investigation of trimethylsilyl- and t-butyl-thiophenes

Penning ionization electron spectroscopy and CNDO/S calculations have been successfully applied to the analyses of the UV photoelectron spectra of 2- and 2,5-bistrimethylsilylthiophene and 2-t-butylthiophene. The relative intensities of the π type bands are greatly enhanced in the Penning spectra compared with those of the UV photoelectron spectra.     

The interaction of metastable Ne(3s 3 P 2,3 P 0) atoms with alkali atoms

Using crossed beams of alkali atoms (Li, Na, K) and state-selected metastable Ne(3s ³ P ₂,³ P ₀) atoms, we have measured the energy spectra of electrons resulting in the respective Penning ionization processes at thermal collision energies. The spectra are very different for Ne(³ P ₂) and Ne(³ P ₀): those for Ne(³ P ₂) are broad due to a strongly attractive interaction potential with a well depth of 798 (30) meV (Li), 672(20) meV (Na), and 561(20) meV (K), those for Ne(³ P ₀) are narrow and compatible with van der Waals type attraction (well depth <50 meV). The Ne(³ P ₂) cross section exceeds the one for Ne(³ P ₀) by about an order of magnitude.     

à 2A1 → X̃ 2B1 emission spectrum of cis-1,2-difluoroethylene cation and the non-radiation decay of the à states of the haloethylene cations in the gaseous phase

The results of the search for the à → X? radiative relaxation of haloethylene cations in the gaseous phase are reported. Only in the case of cis-1,2-difloroethylene cation was an emission spectrum detected. It is identified as the à ²A₁ → X? ²B ₁ band system on the basis of photoelectron spectroscopic measurements. An assignment of the emission bands yields the vibrational frequencies of four of the A₁ fundamentals (under C₂, symmetry) for the X? state and one for the à state. Well resolved Ne(I) photoelectron spectra of cis- and trans-1,2-difluoroethylene are presented, from which some vibrational frequencies for these cations in the X? and à states are also obtained. The lifetimes of cis-1,2-difluoroethylene cation in the lowest vibrational levels of the à ²A₁ state have been measured. The decay of this cation is unusual as these levels are depleted both by, radiative, and pathways leading to fragment ions (C₂HF⁺). The lack of detectable emissions with other fluoro-, chloro- and bromo-ethylene cations is discussed and the likely symmetries of the à states are proposed.     

Photoelectron spectra of quaternary salts in solution

The ionisation energies, measured by He(I) photoelectron spectroscopy, are reported for I^?, Cl^?, Br^?, CNS^? and NO^?₂ in adiponitrile solution. These energies give a straight line when plotted against the energies of the electron transfer to solvent absorption bands of the ions in acetonitrile solution. The intercept gives the electron affinity of the solvent; for acetonitrile, assumed to be spectroscopically equivalent to adiponitrile, the electron affinity is found to be 1.85 eV; for water it is 1.65 eV. The energies of electron transfers not observable in the UV absorption spectrum of NO^?₂ solutions are estimated from the photoelectron spectra.     

Angle-dependent electron energy spectra resulting from autoionizing Ne⋆ (3s 3 P 2) +H(12 S) collisions

Experimental angle-dependent electron energy spectra for the autoionization complex Ne*(3s ³ P ₂)+H(1² S), leading to Penning and associative ionization, are reported. The data, measured at thermal collision energies (ē _rel～51 meV), clearly show an angular variation of the spectral shape, indicating that electrons with angular momentuml>0 participate in the autoionization process. The corresponding non-isotropic electron emission leads to a correlation between the impact parameter-dependent heavy-particle dynamics and the observed electron energy spectrum at a certain detection angle. The experimental results are qualitatively discussed in connection with previous work on the system He*(2³ S)+H(1² S). Furthermore, we present quantum mechanical model-calculations for the electron energy spectrum on the basis of available potential data.     

Isotopically resolved {ie30-01} electronic spectrum of Ag3 and calculation of its Jahn-Teller effects

Ag₃ was produced by pulsed-nozzle laser vaporisation and jet-cooled in a Ne supersonic expansion. Onecolor resonant two-photon ionisation (R2PI) spectra of the {ie30-02} transition of Ag₃ were separately measured for all four isotopic combinations. Long vibrational progressions are observed, involving clearly resolved bands at low energy, merging into a dense but resolvable spectrum up to 1000 cm¹ above the origin. Both the ground {ie30-03} and excited {ie30-04} states of Ag3 are susceptible to Jahn-Teller distortion along the degenerate e′ bending coordinate. The Jahn-Teller analysis includes both linear and quadratic terms, simultaneously with the spin-orbit coupling. Following extensive parameter fitting, the absorption spectrum is calculated, and bands assigned. The spin-orbit splitting is quenched below the localization energy, but becomes observable ≈ 300 cm^-1 above the origin.     

The absorption spectrum of the perfluoropyridine cation in a Ne matrix

The first resolved, optical absorption spectrum for any azabenzene molecular ion is reported. The spectrm of C₅F₅N⁺ has been obtained in a Ne matrix. The observed bands are tabulated and the spectrum analyzed to obtain vibrational frequencies for the B? electronic state.     

Valence States of Lead and Bismuth Atoms in the High-Temperature Superconductor BaPb1-xBixO3

X-ray photoelectron spectra of valence bands and core levels of BaPb_0.8Bi_0.2O₃, PbO, PbO₂, BaPbO₃, BaBiO₃, NaBiO₃, and Bi₂O₃ were studied. Comparison of the electron binding energies of the Pb 4f7/2 or Bi 4f7/2 core levels for all the oxides studied showed that the high-temperature oxide superconductor BaPb_0.8Bi_0.2O₃ contains simultaneously two different valence forms of lead atoms (Pb^IV and Pb^II) and two different valence forms of bismuth atoms (Bi^V and BiIII). Parameters of the X-ray photoelectron spectra of the valence bands do not contradict the conclusion on heterovalent states of lead and bismuth atoms in BaPb_0.8Bi_0.2O₃.     

High-resolution photoelectron spectrum of ozone

The photoelectron spectra of ozone have been recorded and the first three electronic band systems reassigned on the basis of observed vibrational structure and calculations reported in the literature. The systems X?,Ã, and B? at 12.75, 13.03, and 13.57 eV are assigned as ²A₁, ²A₂, and ²B₂, respectively.     

Theoretical and experimental study of the vacuum ultraviolet spectrum of tetrasubstituted tin derivatives SnCl4 and Sn(CH3)4

The vacuum ultraviolet spectra of two tetrasubstituted tin derivatives (SnCl₄ and Sn(CH₃)₄) have been recorded down to 110 nm. Ab initio CI calculations led to a satisfying interpretation of the electron and photoelectron spectra. The first two bands of SnCl₄, at 201 and 163 nm, are attributed to (n → σ and σ → σ) valence transition, while the first band of Sn(CH₃)₄, at 186 nm, presents a pure Rydberg character, as in the case of SnH₄. The rest of the spectrum can be attributed to Rydberg transitions mixed with valence states to varying extents.     

Characterization of Au-Rh/TiO2 catalysts by CO adsorption; XPS, FTIR and TPD experiments

On X-ray photoelectron spectra of the Au-Rh/TiO₂ catalysts the position of Au4f peak was practically unaffected by the presence of rhodium, the peak position of Rh3d, however, shifted to lower binding energy with the increase of gold content of the catalysts. Rh enrichment in the outer layers of the bimetallic crystallites was experienced. The bands due to Au⁰-CO, Rh⁰-CO and (Rh⁰)₂-CO were observed on the IR spectra of bimetallic samples, no signs for Rh⁺-(CO)₂ were detected on these catalysts. The results were interpreted by electron donation from titania through gold to rhodium and by the higher particle size of bimetallic crystallites.     

Photoelectron spectrum of NO2−: SAC-CI gradient study of vibrational-rotational structures

Three-dimensional accurate potential energy surfaces around the local minima of NO₂⁻ and NO₂ were calculated with the SAC/SAC-CI analytical energy gradient method. Therefrom, the ionization photoelectron spectra of NO₂⁻, the equilibrium geometries and adiabatic electron affinity of NO₂, and the vibrational frequencies including harmonicity and anharmonicity of NO₂⁻ and NO₂ were obtained. The calculated electron affinity was in reasonable agreement with the experimental value. The SAC-CI photoelectron spectra of NO₂⁻ at 350 K and 700 K including the rotational effects were calculated using the Franck–Condon approximation. The theoretical spectra reproduced well the fine experimental photoelectron spectra observed by Ervin et al. (J. Phys. Chem. 1988, 92, 5405). The results showed that the ionizations from many vibrational excited states as well as the vibrational ground state are included in the experimental photoelectron spectra especially at 700 K and that the rotational effects are important to reproduce the experimental photoelectron spectra of both temperatures. The SAC/SAC-CI theoretical results supported the analyses of the spectra by Ervin et al., except that we could show some small contributions from the asymmetric-stretching mode of NO₂⁻. © 2018 Wiley Periodicals, Inc.     

An interpretation of the O2 Auger electron spectrum

The Auger electron spectrum of O₂ is interpreted by comparing with other spectra, such as the photoelectron spectrum, the electron impact mass spectrum, and the double charge transfer spectrum. Each of these four spectra obeys its own selection rule; the difference in the selection rules plays a key role in our interpretation. Auger decays following a core shake-up excitation are identified in the O₂ spectrum for the first time. Many of the previous assignments are revised.     

Diatomic potential well depths from analyses of high-resolution electron energy spectra for autoionizing collision complexes

High-resolution energy spectra of electrons released in Penning ionization collisions of metastable rare gas atoms Rg*(ns) (Rg = He, Ne, Ar, Kr, Xe) with several open-shell and closed-shell atoms are analyzed to determine the well depth of the potential energy curve which describes the respective autoionizing collision complex. We thereby elucidate trends in the chemical interaction of Rg* with closed-shell target atoms A(ns ²) and establish a basis for detailed comparison with the respective interactions involving open-shell, ground state alkali atoms A(ns). From electron energy spectra due to␣associative ionization (RgH⁺ formation) in Rg* + H(1s) collisions, we determine binding energies for the RgH⁺(¹Σ) ground state potential (Rg = Ne, Ar, Kr, Xe) with uncertainties around 0.03 eV. Received: 30 June 1998 / Accepted: 5 August 1998 / Published online: 28 October 1998     

Optogalvanic study of A Ne/O2 glow discharge

We present a partial mechanism for excitation and energy transfer in a Ne/O₂ dc discharge. Atomic and molecular concentrations are monitored via the optogalvanic effect. A resonant Penning ionization process is proposed for the production of O₂⁺(a⁴Π_ut, υ = 3). An optogalvanic signal, due to atomic oxygen, can be used to monitor oxygen at levels as low as 100 ppm.     

The state dependence of the interaction of metastable rare gas atoms Rg*(ms3 P 2,3 P 0) (Rg=Ne,Ar, Kr,Xe) with ground state sodium atoms

Using crossed beams of metastable rare gas atoms Rg*(ms³ P ₂,³ P ₀) (Rg=Ne, Ar, Kr, Xe) and ground state sodium atoms Na(3s ² S _1/2), we have measured the energy spectra of electrons released in the respective Penning ionization processes at thermal collision energies. For Rg*(³ P ₂)+Na(3s), the spectra are quite similar for the different rare gases, both in width and shape; they reflect attractive interactions in the entrance channel with well depthsD* _e [meV] decreasing slowly from Rg=Ne to Xe as follows: 676(18); 602(23); 565(26); 555(30). For Rg*(³ P ₀)+Na(3s), the spectra vary strongly with the rare gas, indicating a change in the character of the interaction from van der Waals type attraction (Ne) to chemical binding for Kr and Xe with well depthsD* _e [meV] of: 51(19); 107(25); 432(30); 530(50). These findings are explained through model calculations of the respective potential curves, in which the exchange and the spin orbit interaction in the excited rare gas and the molecular interaction between the two valences-electrons in terms of suitably chosen singlet and triplet potentials are taken into account. These calculations also explain qualitatively the experimental finding that the ratiosq ₂/q ₀ of the ionization cross sections for Rg*(³ P ₂)+Na and Rg*(³ P ₀)+Na vary strongly with the rare gas from Ne to Xe as follows: 15.8(3.2); 2.6(4); 1.4(2); 1.6(4).     

Chemical shifts of auger electron lines and electron binding energies in free molecules. Sulfur compounds

The first paper describing a series of systematic investigations of the chemical shifts in Auger electron spectra from various free molecules is presented. Excitation is performed by means of a fine focus electron beam. The Auger electrons are retarded in a four component lens system and recorded at high resolution in a new multidetector system placed in the focal plane of the ESCA instrument. A calibration procedure against the KL₂L₃ Auger electron line of Ne is described. The first study concerns Auger electron line shifts for sulfur in some small molecules and the results are compared to the corresponding chemical shifts in the core photoelectron spectra. A formalism based on a transition potential model is briefly presented which takes account of the relaxation energies involved in Auger transitions as well as in single photoionization.     

Enhancement of vibrational level population of N2 and CO by photoelectron spectrometry

Photoionization of N₂ and CO by 736–744 Å doublet lines from a Ne I resonance discharge gives photoelectron spectra which show that all vibrational levels of N₂⁺, X²Σ_g⁺, and CO⁺, X²Σ⁺, situated below the ν′ = 0 level of the first excited ionic state, are populated. An autoionizing mechanism is proposed to interpret this result, as in the case of O₂ and NO.