Angle-resolved photoelectron spectra of ethylene as a function of photon energy using synchrotron radiation

As a test of the applicability of multiple-scattering theory to an unsaturated organic system, angle-resolved photoelectron spectra of the first four bands of ethylene have been measured from 1.5 eV above threshold to a photon energy of 28 eV. The results are compared to the multiple-scattering theory calculations of Grimm. The comparisons are excellent except for the 1 b_3u orbital below 14 eV, and the disagreement is attributed to the occurrence of autoionization. It is found that the π orbital has a much higher β value than the σ orbitals, but the β value for the π orbital varies more rapidly than that for the σ orbitals from threshold to ～0.5 Rydberg (～7 eV).     

Characterisation of thin films of bismuth oxide by X-ray photoelectron spectroscopy

The XPS (or ESCA) technique has been used for the characterisation of vacuum-deposited thin films of bismuth oxide. The spectra of Bi metal and Bi₂O₃ powder are used for comparison. The characterisation is carried out by consideration of the positions of the Bi 4f_{$\text{7}\text{2}$} and 4f_{$\text{5}\text{2}$} peaks and by using peak-fitting routines. A lower suboxide of bismuth, and metallic bismuth are observed in bismuth oxide films as evaporated. Oxidation of these films by heating in air results in bismuth(III) oxide. A linear relation is found between the binding energies and oxidation state. The corresponding O 1s spectra for the two types of film are also discussed.     

High resolution electron energy loss spectroscopy of fatty acids prepared by langmuir-blodgett techniques on polycrystalline silver

The surface of monomolecular layers of fatty acids prepared by Langmuir-Blodgett methods on polycrystalline silver has been studied by High Resolution Electron Energy Loss Spectroscopy (HREELS). Results demonstrate HREELS sensitivity to large molecules in molecular organizates on polycrystalline substrates. Spectra are interpreted in comparison with infrared vibrational data; results allow differentiation of degrees of unsaturation. The carbonyl vibration loss is observed as a weak feature, explained as due to the orientation of the fatty acid heads “down” on the subtrate surface approximately 20 Å from the scattering interaction.     

The electronic structure,x-ray photoelectron and emission spectra of YOF

The results of electronic structure calculations for YOF are presented, making use of Xα-DVM together with experimental X-ray photoelectron and emission spectra for this compound. Three versions of calculations have been performed, depending on the relation between oxygen and fluorine charges in the [YO₄F₄] cluster. The interpretation of experimental spectra is carried out on the basis of these calculations.     

Infrared absorptivity of the 9.6 μm ozone band as a function of spectral resolution and abundance

The i.r. absorptivity of the R-branch maximum (9.48 μm) of gaseous ozone was determined at 25°C as a function of spectral resolution and absorbance a/a total pressure of 735 torr of dry air. Ozone samples produced by a high voltage discharge in oxygen, and measured accurately by either a pressure or volume change, were spectroscopically measured in a 57741. environmental chamber at paths up to 69.17 m. A linear relation between spectral slit (Δv) and the ratio of the absorbances (R_v/p) of the observed absorption minimum between the R and Q branches to the absorption maximum of the R-branch was found for cm^-1 < Δv < 10cm^-1 and for absorption up to 48%. The i.r. absorptivity varied approx. 20% (from 3.9 to 4.8 cm^-1 STP) over the range of values for R_v/p studied. Absorptivity was weakly dependent on ozone abundance (w) for w?0.03 cm STP.     

The photoelectron spectra of some heterocyclic compounds which contain N,O, Cl and Br

The photoelectron spectra of 19 heterocyclic compounds, several of which are germicidal agents, containing N, O, Cl and Br have been investigated. Complete band assignments have been made for the lone-pair regions of the spectra for future reference in structure/biological-activity correlations. A detailed comparison of the carbonyl-oxygen lone-pair splitting patterns in the spectra indicates that succinimide is skeletally planar, while N-chlorosuccinimide and N-bromosuccinimide are substantially nonplanar in the gas phase.     

The photoelectron spectra of some iron tricarbonyl complexes of 4π-electron donor ligands

The photoelectron spectra of eighteen compounds which are dienes or diene—iron tricarbonyl complexes have been investigated. A comparison of the photoelectron spectra of the dienes and corresponding iron carbonyl complexes has yielded the values of the perturbation energies for the two π orbitals of the diene moiety caused by interaction with Fe(CO)₃. These perturbation energies are relatively constant (Δπ₁ = 0.89 ± 0.07 eV, Δπ₂ = 0.22 ± 0.06 eV) throughout the series. They have been employed to estimate the π ionization energies of the organic transient species cyclobutadiene (8.29 and 11.95 eV) and trimethylenemethane (8.36 and 11.79 eV), two novel molecules which have not been studied successfully by photoelectron spectroscopy to date.     

Raman spectroscopy of solid nitrogen up to 374 kbar

We measured the Raman spectrum of room-temperature solid nitrogen in a diamond cell at pressures up to 374 kbar. Only the molecular stretching mode was observed. The frequency of this mode appears to increase smoothly from 2340 cm^-1 at 39 kbar to 2394 cm^-1 at 374 kbar. Between about 50 and 120 kbar, the Raman line is split into a second, higher-frequency peak, which may be associated with molecular ordering in the solid. Measurements of broadening and splitting in fluorescence lines from the ruby pressure gauge indicate that solid nitrogen is reasonably plastic up to 130 kbar. We suggest that nitrogen might serve as a useful pressure medium.     

Study of the phase transitions in ammonium bromide by Raman spectroscopy

A complete Raman scattering study of an oriented NH₄Br single crystal has been carried out and new results are reported for temperature between 45 to 410°K. The study includes measurements and interpretations of the Raman spectral bandwidths, intensities and frequencies of the lattice and internal modes as a function of temperature. Because of the ability of generating a single domain crystal, unambiguous assignments of the Raman active modes are made. From the present data together with those presented previously significant information on the behavior of the ordering and crystal structure associated with the phase transitions in NH₄Br is obtained.     

New method for photoelectron spectroscopy of solutions

A new method of rather general scope is reported for the determination of the photoionization (PI) spectra of solutions. Spectra thus obtained correspond to PI for ejection of quasi-free electrons into the liquid phase. The method is based upon photoelectron emission (PEE) into vacuum by the solution upon irradiation with adjustable photon energy. A new instrument is described which features irradiation (up to 10 eV) of a film of the solution on the rim of a rotating disk target (72 r.p.m.). Two types of data are obtained: PEE quantum yield per incident photon as a function of photon energy; energy distribution curve (EDC) of electrons emitted into vacuum at given photon energies. The PI cross-section is obtained as a function of photon energy by the previously developed method of EDC superposition. The method is applicable even when the contribution by the solvent to total PEE is dominant. Application is made to PI by 0.4 M indole in glycol for irradiation from 6.5 to 10 eV. Experimental results include: the effect of equilibrium vapor pressure (3.5 × 10^?3 ? 4.6 × 10^?2 torr) on EDC's; PEE spectral response of solvent and solution; EDC's from 6.5 to 10 eV. Interpretation covers these results and also includes: attenuation of the photon flux in the gas phase; PI in the gas phase; changes of temperature and solute concentration caused by evaporation. The PI spectrum of indole in glycol at ?7 °C exhibits a band for bound-continuum transitions (rising segment up to ≈ 7.0 eV) and a superimposed band (maximum at ≈ 7.6 eV) for PI via autoionization of excited bound states. Systematic development of the photoionization spectroscopy of solutions up to 10 eV is made possible by this approach. Application of the rotating disk methodology to higher photon energies (HeI, ESCA) may be of interest.     

The conformational analysis of 1-haloalkanes by low resolution microwave spectroscopy

The low resolution microwave spectra of a series of 1-haloalkanes were studied. With the exception of 1-bromobutane only the all s-trans conformer and those gauche conformers in which a single dihedral angle is gauche were foud. By analyzing data from a homologous series, a gauche dihedral angle of 286 ± 4° was determined for the gauche conformers of the bromo and iodo species. An analysis of relative intensities of the 1-bromobutane and 1-iodobutane bands yielded standard Gibbs free energy differences.     

Gas phase and solid state X-ray photoelectron spectra of the substituted acetylenes (SF5)n C2 (CF3)2−n (n = 0, 1, 2): A comparison of the pentafluorosulfur and trifluoromethyl groups

The core level X-ray photoelectron spectra (XPS) of CF₃CCCF₃, CF₃CCSF₅ and SF₅CCSF₅ have been measured in the solid state. Gas phase spectra of CF₃CCCF₃ and CF₃CCSF₅ have also been obtained. The XPS data, interpreted with the point charge potential model and semiempirical MNDO (minimum neglect of differential overlap) molecular orbital calculations, indicate that the electron withdrawing effect of the ?CF₃ group is greater than that of the ?SF₅ group. Results further suggest that sulfur 3d orbitals do not play a detectable role in the bonding or charge distribution in these molecules. Carbon 1s linewidths of ?CF₃ carbon atoms are found to be much narrower than those arising from the acetylenic carbon atoms. The narrower lines correlate with the much higher binding energy of the ?CF₃ carbon atoms. Large shifts (nearly 1 eV) in heteroatom core level binding energy differences (for example, F 1s — C 1s) between the gas phase and solid state data are observed. These shifts are attributed to solid state effects (Madelung potential, intermolecular bonding interactions, and/or extramolecular relaxation contributions). From these comparisons it is clear that solid state effects are not uniform in their influence on the photoionized sites in these molecules.     

New depth-profiling method by angular-dependent x-ray photoelectron spectroscopy

A non-destructive method for depth profiling by X-ray photoelectron spectroscopy, based on the dependence of the analysed depth with the electron emission angle, is presented.The extraction of the concentration profile from angular distribution experiments is achieved, in the framework of a flat-layer model, by minimizing the difference between theoretical and experimental relative intensities. The applicability and limitations of the method are discussed on the basis of computer simulation results. In particular, constraints reflecting the physical properties of the system must be introduced in the numerical treatments. The depth probed is of the order of 3λ, λ being the value of the inelastic mean free path, and the depth resolution is of the order of λ/3. In tests of the method, the concentration depth profiles of the Ag-Al₂O₃ and the SiO₂-Si interfaces and of the surface region of a Cu-Ni alloy have been obtained.     

Angle-resolved photoelectron measurements on the first two orbitals of acetylene using synchrotron radiation

The angle-resolved photoelectron spectrum of acetylene has been measured using synchrotron radiation over a range of photon energies from 12 to 28 eV.     

Mössbauer emission spectroscopy of doped 57Co1−xO—I. Acceptor impurities: 57Co1−xO:Li

Mossbauer emission studies on Li-doped ⁵⁷Co_1?xO have been carried out It is shown that the number of Co vacancies as well as the number of L1⁺ impurities entering the lattice determine the Fe³⁺ fraction in the emission spectra A recombination model based on the acceptor character of the defects existing in the lattice is proposed This model reproduces well all the Mossbauer data.     

Mössbauer emission spectroscopy of doped 57Co1−xO—II. donor impurities: 57Co1−xO:Fe,Ti, In

Mossbauer emission studies of Fe, In, and Ti doped ⁵⁷Co_1?xO have been earned out The appearance of the anomalous ferrice line is due to the existence of cationic vacancies and impurity acceptor levels An electron recombination model is proposed which takes into account the electronic character of the impurity defects.