X-Ray photoelectron spectroscopic study of schiff base metal complexes

Metal donor atom core electron binding energies have been measured for seven related polydentate Schifr base complexes of nickel(II) and copper(II). The potential donor atoms of all neutral ligands except one and the free metals were also studied. Rather high metal chemical shifts were observed, but no correlation between metal binding energy and known ligand field strength was noted. Satellite peaks are found in the spectra of all paramagnetic complexes.     

A photoelectron spectroscopic study of the carburization of MoO3

MoO₃ and Mo samples containing copper were treated with different hydrocarbon/hydrogen gas mixtures. The formation of Mo₂C was followed by X-ray photoelectron spectroscopy (XPS). Spectra taken in the Mo 3d, C 1s, O 1s, Cu 2p and Cu KLL regions demonstrated that the treatment with the hydrocarbon/hydrogen gas mixtures led to the formation of Mo₂C. From the comparison of the effects of various hydrocarbons on the XP spectra of Mo 3d we can state that the reduction of MoO₃ starts at the lowest temperature for C₂H₆/H₂ (600 K) followed by CH₄/H₂ (700 K) and C₄H₁₀/H₂ (723 K). Binding energies of Mo 3d_5/2 characteristic for Mo₂C are measured in the range of 227.7-228.0 eV. These values were attained at 900 K for CH₄/H₂, at 800 K for C₂H₆/H₂ and at 873 K for C₄H₁₀/H₂. Addition of copper to MoO₃ catalyzed its reduction and promoted the carburization process.     

The HeI photoelectron spectra of methyl-substituted 1,2,4-pentatrienes (vinylallene)

The HeI photoelectron spectra of trans-1,2,4-hexatriene(1), 4-methyl-1,2,4-pentatriene(2), 3-methyl-1,2,4-pentatriene(3), 1,3,4-hexatriene(4) and 3,4-dimethyl-1,2,4-pentatriene(5) have been obtained and interpreted. LCBO and CNDO/S calculations indicate for the highest energy orbitals a π,π,π,σ sequence as in 1,2,4-pentatriene. The effect of methyl substitution on the three π orbitals is analyzed.     

A photoelectron spectroscopic study of benzonitrile,ethynylbenzene and some of its substituted derivatives

The He-I photoelectron-spectra of ethynylbenzene and benzonitrile have been reinvestigated. An assignment is given to the low lying ionization potentials as well as of those ranging up to 21 eV, which were not accounted for in previous work³. Furthermore, the He-I photoelectron-spectra of some ω- and para-substituted ethynylbenzenes are discussed. A close inspection of the vibrational structure associated to the third ionization potential of ethynylbenzene and its ω-deutero-derivative clearly shows the quasi-π-orbital to be highly localized on the acetylenic triple bond.     

A photoelectron spectroscopic investigation of the electronic structure of trimethylsilylhaloacetylenes

The photoelectron spectra (He I excitation) of trimethylsilylacetylene M(H) and of the four trimethylsilylhaloacetylenes M(X) with X = F, Cl, Br, I hav     

Vacuum UV photoelectron intensity of gaseous compounds: I. HeI spectra of simple compounds

A new method for determining absolute photoionization cross sections for gaseous compounds is proposed. In this method a mixture of a sample and a standard gas (N₂) is used in photoelectron intensity measurements so that the relative intensity of the component is obtained with respect to N₂ The relative photoelectron band area is converted to the absolute photoionization cross section on the basis of the absolute cross-section data of N₂ recently reported by Samson et al. This method has been applied to various aliphatic compounds to study the effect of alkyl substitution on photoionization cross sections of O- and N-nonbonding electrons for 584-Å radiation.     

A photoelectron spectroscopic study of the adsorption of CO and CO2 on platinum

The adsorption of CO and CO₂ on platinum has been studied by UV photoelectron spectroscopy using both He I and He II radiation. The modulation of the intensity of the spectral features observed for adsorbed CO as the photon energy is changed is used to assign the observed levels. The results are in reasonable agreement with recent theoretical and experimental work. The levels are observed to shift by different amounts compared to gas phase CO because of chemical binding effects. The adsorption of CO₂ produces spectral features that are shifted by the same amount compared to gas phase CO₂. This, together with the absence of any localized attenuation of the platinum valence band and the low heat of adsorption, indicates that CO₂ is physisorbed on platinum.     

An Auger and X-ray photoelectron spectroscopic study of sodium metal and sodium oxide

Photoelectron and Auger electron measurements have been made on polycrystalline films of sodium metal evaporated in ultra high vacuum, and on Na₂O produced by in-situ oxidation by dry oxygen. Most of the spectra were recorded using Mg Kα (1254 eV) radiation but excitation by 5 keV electrons or monochromatized Al Kα (1487 eV) X-rays was used for specific purposes. Core and valence electron binding energies, photoionization cross-sections relative to Na 1s, KLL and KLV Auger energies and transition probabilities are reported. Energy losses in the metal and oxide are discussed and the relative intensities of surface and bulk plasmon losses have been used to calculate mean electron escape depths in the metal. When corrections were made for experimental geometry, escape depths of 10 Å at 180 eV and 31 Å at 1200 eV were obtained. An escape depth of 23 Å at 980 eV was obtained by Na 1s-Na K-Auger intensity correlation and this is consistent with the plasmon data. Data on Auger satellite lines are presented and, in particular, evidence has been obtained which indicates that a high energy satellite should not be attributed to a plasmon gain mechanism. Valence band influences on the KLV Auger spectra are discussed with reference to the XPS spectrum and other sources of valence band information. Unexpected structure was found in the KLV spectra of the metal which, pending thorough interpretation, offsets the sensitivity and resolution advantages which these spectra otherwise offer for valence band studies.     

X-ray photoelectron spectroscopic study of nitrogen incorporated amorphous carbon films embedded with nanoparticles

The effect of substrate bias on X-ray photoelectron spectroscopy (XPS) study of nitrogen incorporated amorphous carbon (a-C:N) films embedded with nanoparticles deposited by filtered cathodic jet carbon arc technique is discussed. High resolution transmission electron microscope exhibited initially the amorphous structure but on closer examination the film was constituted of amorphous phase with the nanoparticle embedded in the amorphous matrix. X-ray diffraction study reveals dominantly an amorphous nature of the film. A straight forward method of deconvolution of XPS spectra has been used to evaluate the sp³ and sp² contents present in these a-C:N films. The carbon (C 1s) peaks have been deconvoluted into four different peaks and nitrogen (N 1s) peaks have been deconvoluted into three different peaks which attribute to different bonding state between C, N and O. The full width at half maxima (FWHM) of C 1s peak, sp³ content and sp³/sp² ratio of a-C:N films increase up to −150 V substrate bias and beyond −150 V substrate bias these parameters are found to decrease. Thus, the parameters evaluated are found to be dependent on the substrate bias which peaks at −150 V substrate bias.     

Reaction of selenite with biochemically active thiols: An X-ray photoelectron spectroscopic study

The usefulness of X-ray photoelectron spectroscopy for electron transport studies was shown by examining the reaction of selenite with mercapto-ethanol     

An X-ray photoelectron spectroscopic study of some nickel (II) amine complexes

The X-ray photoelectron (XPS) spectra of several Ni(II) diamine complexes, a Ni(II) triamine complex and several Ni(II) diimine complexes are reported in terms of the Ni 2p, Cl 2p and N 1s core level binding energies. Theoretical models are presented to account for the quadratic relationship observed between XPS Ni 2p_{$\text{3}\text{2}$}binding energy shifts and the N-H infrared rocking frequency as related to these complexes. On the basis of this correlation, it is possible to discriminate between free counter-ions coordinated to the metal or involved in cluster-ion formation. Individual XPS data for these complexes are interpreted in terms of the intrinsic nature of the metal environment and an attempt is made to calculate the metal and donor nitrogen atomic charges for selected complexes.     

Determination of the kinetic parameters of the isomerization reaction of ethyl isocyanide using HeI photoelectron spectroscopy

The use of HeI photoelectron spectroscopy (PES) for the kinetic study of chemical reactions was introduced previously by us. As another example of the determination of the kinetic parameters of a chemical reaction using the PES method, the isomerization reaction of ethyl isocyanide CH₃CH₂NC → CH₃CH₂CN is investigated. It is found to be first order and the kinetic equations at 193.6, 200.0 and 210.3°C can be expressed as ln R_{466.6 K} = − (7.600 ± 0.026) × 10⁻⁵t − 0.4350; ln R_{473.0 K} = − (1.329 ± 0.032) × 10⁻⁴ − 0.4375 and ln R_{483.3 K} = − (3.170 ± 0.052) × 10⁻⁴ − 0.4354, respectively. The rate constants of the reactions at 193.6, 200.0 reactions at 193.6, 200.0 and 210.3°C are respectively (7.600 ± 0.026) × 10⁻⁵, (1.329 ± 0.032) × 10⁻⁴ and (3.170 ± 0.052) × 10⁻⁴ s⁻¹. The calculated activation energy (E_a) of this isomerization reaction is 38.36 ± 0.32 kcal mol⁻¹. These results are also in excellent agreement with the results obtained by a traditional method. This means that PES is a valuable method for determining the kinetic parameters of chemical reactions. The value of the intercept in the kinetic equations is related to the logarithm of the ratio of the photoionization cross-section of the bands used. This also means that the relative photoionization cross-sections of the bands used for the sample studied are obtained in the kinetic study of a chemical reaction using the PES method.     

Peak overlaps and corresponding solutions in the X-ray photoelectron spectroscopic study of hydrodesulfurization catalysts

Al₂O₃-SiO₂-based Co(Ni)-Mo(W)-S catalysts are widely investigated hydrodesulfurization (HDS) catalysts in recent decades. XPS is a suitable technique to detect the surface properties of HDS catalysts. Typical overlapping spectra in the XPS analysis of HDS catalysts, such as Mo3d and S2s, Si2p and bremsstrahlung-induced Al KL₂₃L₂₃ using nonmonochromatic AlKα source, W4f and W5p_3/2, as well as the disturbance of Auger lines on Ni2p and Co2p, are carefully studied in the present paper. Besides, effective methods to overcome the influence of peak overlaps are illustrated. These results would provide basic and important information in interpreting XPS results of HDS catalysts.