X‐ray photoelectron spectroscopy studies of chromium compounds

Photoelectron spectra of a number of chromium oxides and other compounds were studied under high spectral resolution conditions chosen to reduce the possibility of differential charging. Some of the suite of Cr(III) compounds chosen for study produced Cr 2p spectra containing fine structure that could be identified with multiplet splitting. The splitting patterns produced were similar for all trivalent binary and ternary oxides and sulphides whose patterns closely reproduced the splitting predicted for the Cr(III) free ion by Gupta and Sen. The fine structure observed for compounds such as chromium (III) chloride had a distinctly different pattern. A number of other chromium (III) compounds were studied that did not exhibit the fine structure described above; nonetheless, well‐defined line shapes and reproducible peak centroids were obtained by fitting protocols. The use of such information to determine surface chemistry on chromated steels is described, based on the spectral knowledge of chromium (III) oxides and hydroxides and the chromium (VI) oxide systems. Copyright © 2004 John Wiley & Sons, Ltd.     

Studies of degradation behaviors of poly (3‐hexylthiophene) layers by X‐ray photoelectron spectroscopy

Degradation behaviors of poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) layers on NiO in the presence of H₂O at ambient pressure and dark conditions were studied using X‐ray photoelectron spectroscopy (XPS). Upon H₂O exposure at 120 °C, partial oxidation of P3HT together with molecular water incorporation, but with the maintained local ring‐structure, were deduced by XPS. Valence band spectra of XPS evidenced that the partial oxidation of P3HT local structure could alter π‐conjugation systems of P3HT layers, forming additional electronic states close to its original highest occupied molecular orbital. For comparison, P3HT surface was also exposed to O₂, and no change in the S 2p and C 1s spectra was found by O₂ exposure at 120 °C, implying that H₂O plays a major role at the initial stage of P3HT oxidation. Copyright © 2014 John Wiley & Sons, Ltd.     

Comparative X‐ray study of three nickel(II)–thio­cyanate compounds

Three cis nickel–di­thio­cyanate (SCN) complexes with different N,N′‐bidentate bases have been prepared and their crystal structures determined: bis(2,2′‐bi­pyridine‐N,N′)­bis­(thio­cyan‐­ato‐N)­nickel(II), [Ni(SCN)₂­(C₁₀H₈N₂)₂], bis(1,10‐phen­anthroline‐N,N′)­bis­(thio­cyanato‐N)­nickel(II), [Ni(SCN)₂­(C₁₂H₈N₂)₂], and bis(2,9‐di­methyl‐1,10‐phenanthroline‐N,N′)­bis­(thiocyanato‐N)nickel(II) mono­hydrate, [Ni(SCN)₂­(C₁₂H₈N₂)₂]·H₂O. Distortions due to ligand size are discussed.     

Synthesis and X‐ray crystal structures of hypervalent arsenic compounds bearing arsenic‐iron bonds

A hypervalent arsorane with an As–Fe bond [ 6 : Rf₂As*FeCp(CO)₂ (Rf: o‐C₆H₄C(CF₃)₂O‐)] was synthesized by the reaction of the arsoranide anion ( 4‐Et ₄N: Rf₂As*^‐Et₄N⁺) with CpFe(CO)₂I ( 5 ) in the presence of AgBF₄. Diastereomeric arsoranes { 7a and 7b : Rf₂As*Fe*Cp(CO)(PPh₃)} were prepared by irradiation of 6 with a tungsten lamp in the presence of triphenylphosphine. X‐ray crystallographic analysis of 6 and 7a showed that the apical As–O bond lengths of these compounds are slightly longer than the equatorial As–C bonds. It is concluded that an electron‐donating group at the equatorial position elongates the apical E–O bond by electron donation to the apical oxygens. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:42–47, 2000     

X‐ray photoemission spectroscopy investigation of Ce1 − xEuxCrO3 nano‐powders

To reveal the surface elemental composition and chemical states of the Ce_{1 ? x} Eu_x CrO₃ nano‐powders (x= 0.0, 0.3, 0.5, 0.7, 0.8, 1.0), X‐ray photoelectron spectroscopy was carried out in two conditions of before and after surface cleaning. This surface characterization described the core level binding energies of cerium, europium and chromium with different oxidation states. These results verified the morphology of the particles' surface which can be a confirmation of the spin disorder in these core‐shell structures. The effect of surface Ar sputtering on the oxidation states were studied. Copyright © 2016 John Wiley & Sons, Ltd.     

X‐ray photoelectron spectroscopic study of Tencel treated with a cationic β‐cyclodextrin derivative

The interaction and the durability to laundering of a cationic β‐cyclodextrin derivative applied to Tencel were examined by x‐ray photoelectron spectroscopy (XPS). The N1(s) XPS spectra of the cationic β‐cyclodextrin treated substrates revealed the presence of the applied finish on the fibre surface and that the durability of the applied finish to hand‐wash was good. However, the cationic β‐cyclodextrin derivative showed poor durability to the ISO CO6/C2S wash protocol. Copyright © 2009 John Wiley & Sons, Ltd.     

Quantitative analysis of saccharides by X‐ray photoelectron spectroscopy

A series of saccharides, including several monohydrates and one amorphous phase, has been investigated by XPS, providing the first database of survey and high‐resolution spectra for this class of compounds. Known stoichiometries and XPS‐determined elemental compositions agree well. XPS has sufficient precision for distinguishing the stoichiometries of mono‐, di‐, and polysaccharides. The C 1s chemical shifts of the acetal and alcohol groups are similar for all samples, albeit with slight binding energy increases in the series from mono‐ to di‐ and polysaccharides. Increasing X‐ray exposure causes a radiation‐induced increase of the aliphatic hydrocarbon emission at 285 eV, concomitant with the appearance of a high binding energy C 1s emission peak at 289.1 eV and a decrease in the O 1s/C 1s emission intensity ratio. Formation of aliphatic hydrocarbon groups is proposed to arise from dehydroxylation, while the increase in the 289.1 eV peak can be attributed to double dehydroxylation at the C₁ position or partial oxidation of an alcohol or acetal group. The rate of radiation damage correlates with previously reported rates of thermally induced caramelization. Copyright © 2009 John Wiley & Sons, Ltd.     

An X‐ray photoemission study of interfacial reaction during annealing of Mg/GaAs(100) interface

In this paper, we present an in situ annealing study on Mg(15 Å)/GaAs(100) interface using X‐ray photoelectron spectroscopy (XPS). The core level results indicate that an interfacial reaction starts between Mg and Ga atoms at room temperature and enhances with annealing. However, at a higher temperature of annealing, a mixed layer of ternary Mg–Ga–As phase is formed at the interface. Corresponding Auger spectra of Mg, Ga and As also show considerable modifications in their nature and therefore support the above reaction. The observed results are correlated and interpreted in terms of continuous changes in electronic and chemical environment at the Mg/GaAs interface. Copyright © 2005 John Wiley & Sons, Ltd.     

Quantitative analysis of complex amino acids and RGD peptides by X‐ray photoelectron spectroscopy (XPS)

The C 1 s, N 1 s, and O 1 s core level binding energies (BEs) of the functional groups in amino acids (glycine, aspartic acid, glutamic acid, arginine, and histidine) with varied side‐chains and cell‐binding RGD‐based peptides have been determined and characterized by X‐ray photoelectron spectroscopy with a monochromatic Al K_α source. The zwitterionic nature of the amino acids in the solid state is unequivocally evident from the N 1 s signals of the protonated amine groups and the C 1 s signature of carboxylate groups. Significant adventitious carbon contamination is evident for all samples but can be quantitatively accounted for. No intrinsic differences in the XP spectra are evident between two polymorphs (α and γ) of glycine, indicating that the crystallographic differences have a minor influence on the core level BEs for this system. The two nitrogen centers in the imidazole group of histidine exhibit an N 1 s BE shift that is in line with previously reported data for theophylline and aqueous imidazole solutions, while the nitrogen and carbon chemical shifts reflect the unusual guanidinium chemical environment in arginine. It is shown that the complex envelopes of C 1 s and O 1 s photoemission spectra for short‐chain peptides can be analyzed quantitatively by reference to the less complex XP spectra of the constituent amino acids, provided the peptides are of high enough purity. The distinctive N 1 s photoemission from the amide linkages provides an indicator of peptide formation even in the presence of common impurities, and variations in the relative intensities of N 1 s were found to be diagnostic for each of the three peptides investigated (RGD, RGDS, and RGDSC). Copyright © 2013 John Wiley & Sons, Ltd.     

X‐ray induced reduction of rhenium salts and supported oxide catalysts

The analysis of Re⁷⁺ compounds has revealed a time‐dependent photoreduction during X‐ray photoelectron spectroscopy (XPS) measurements. Whilst such reduction of metal ions during XPS analysis is not uncommon, this is the first time that cases specifically for rhenium have been identified in the open literature. Copyright © 2016 John Wiley & Sons, Ltd.     

Preparation and X‐ray analysis of potassium (2,3‐dichlorophenyl)glucosinolate

There has been much interest in obtaining crystals for crystallographic analysis of biologically active glucosinolates. Crystals of potassium (2,3‐dichlorophenyl)glucosinolate were obtained as a dual solvate, containing one methanol and one ethanol molecule of crystallization, K⁺·C₁₃H₁₄Cl₂NO₉S₂⁻·CH₃OH·C₂H₅OH. The three‐dimensional polymeric network consists of chains containing the potassium ions coordinated and bridged by sugar O atoms, which run parallel to the a axis and are further crosslinked through the sugar molecules. The channels of this network are occupied by the dichlorophenyl substituents and the ethanol and methanol solvent molecules. The structure of the S‐(2,3,4,6‐tetra‐O‐acetyl‐β‐D‐glucopyranosyl)‐2,3‐dichlorophenylacetothiohydroxymate, C₂₁H₂₃Cl₂NO₁₀S, precursor has also been determined and the β‐configuration and Z isomer of the thiohydroximate substituent is confirmed.     

X‐ray photoelectron spectroscopy study of red oak‐ (Quercus rubra), black cherry‐ (Prunus serotina) and red pine‐ (Pinus resinosa) extracted wood surfaces

The X‐ray photoelectron spectroscopy (XPS) study of black cherry (Prunus serotina), red oak (Quercus rubra), and red pine (Pinus resinosa) wood samples extracted with ethanol, ethanol—toluene, and water was conducted to evaluate chemical modifications occurring on the wood surface due to wood extractives, and derive possible implications for wood utilization. Results obtained indicate an increase in the O/C values following extraction treatments due to the partial removal of high carbon content extractives. The C 1s peaks indicated a decrease in the area of the C1 peak, known to originate from lignin and extractives following extraction. At the same time, a rise in the C₂ peak (mainly originating from cellulose and hemicelluloses) was observed, indicating that more cellulose was exposed on the wood surface following extraction. The O 1s peaks showed an increase in the O₁ peak originating from cellulose, therefore confirming the trend observed for C 1s peaks. These results suggest that extracted wood is more wettable because of the increased exposure of high‐oxygen‐content cellulose molecules, known to be more hydrophilic than lignin and high carbon content extractives. Copyright © 2005 John Wiley & Sons, Ltd.     

Summary of ISO/TC 201 Standard: ISO 16129‐:2012 – Surface chemical analysis — Procedures to assess the day‐to‐day performance of an X‐ray photoelectron spectrometer

This International Standard is designed to allow the user to simply assess, on a routine basis, several key parameters of an X‐ray photoelectron spectrometer. It is not intended to provide an exhaustive performance check but instead provides a rapid set of tests that may be conducted frequently. Aspects of instrument behaviour covered by this document include the vacuum, measurements of spectra of conductive or non‐conductive samples and the current state of the X‐ray source. Other important aspects of the instrument performance (e.g. lateral resolution) fall outside the scope of this standard. The standard is intended for use with commercial X‐ray photoelectron spectrometers equipped with a monochromated Al Kα X‐ray source or with a unmonochromated Al or Mg Kα X‐ray source. Copyright © 2012 John Wiley & Sons, Ltd.     

Interface characterization of a metal‐oxide‐semiconductor structure by biased X‐ray photoelectron spectroscopy

X‐ray photoelectron spectroscopy (XPS) measurements of a Pt/HfO₂(SiO₂)/Si metal‐oxide‐semiconductor (MOS) structure under a bias voltage applied between the gate metal and the silicon substrate were studied. The binding energy shifts of Pt 4f, Hf 4f, O 1s and Si 2p according to the applied voltage were investigated using the MOS structure. After the influence of measurements on the results was carefully examined under various conditions, the amount of the shifts was analyzed from a viewpoint of band alignment. Based on the experimental results, a new way of interpreting the deviation of the electric properties from the ideal ones in a band diagram was proposed. It was demonstrated that the biased XPS is a very powerful method to understand the origin of the electric properties of MOS. Copyright © 2010 John Wiley & Sons, Ltd.     

Electrocapillary Activity and Adsorptive Accumulation of U(VI)‐Cupferron and U(VI)‐Chloranilic Acid Complexes on Mercury Electrode

Interfacial activity of uranium(VI)‐cupferron and uranium(VI)‐chloranilic acid (CAA) complexes (in 0.1 M acetate buffer pH 4.6 or 0.1 M NaClO₄ respectively) on polarized mercury electrode at 110 mV, 10 mV or ?240 mV respectively vs. saturated calomel electrode (SCE), and under conditions of the application of adsorptive stripping voltammetric techniques was studied. It revealed a competitive effect of interfacial activity of the mentioned complexes consisting in a nonmonotonous effect of the bulk concentration of U(VI) on the adsorption of the mentioned complexing reagents at their constant concentrations. At concentrations lower than 5×10^?5 mol L^?1 the complexes U(VI)‐cupferron or U(VI)‐CAA exhibited a relatively strong electrosorption providing the adsorption coefficients β of the order 10⁴ L mol^?1, the maximum surface excess Γ_m ≈ 5 to 10 μmol m^?2 and average Frumkin interaction coefficients reaching their absolute values 2 to 2.6.     

X‐ray photoelectron spectroscopy of miscible poly(methyl methacrylate)/poly(styrene‐co‐acrylonitrile) and immiscible poly(methyl methacrylate)/polyacrylonitrile polymer surfaces metallized by nickel

A miscible blend of poly(methyl methacrylate) and poly(styrene‐co‐acrylonitrile) and an immiscible blend of poly(methyl methacrylate) and polyacrylonitrile were metallized by nickel, and their surfaces were analyzed by X‐ray photoelectron spectroscopy. Before metallization, the heteroatom distribution at the polymer surface was very different in the miscible and immiscible blends. However, this distribution was modified during metallization, which was only possible via polymer‐bond breaking, leading to similar compositions at the two interfaces. Oxygen exhibited a better affinity with nickel than nitrogen, but nickel oxide and nickel nitride were both formed at the interface. Nickel nitride prevented the metal from diffusing into the substrate, playing the role of a barrier, thus driving the oxygen to the metal layer. Amorphous carbon was also detected at the interface as a new carbon species, but it did not have any significant influence on the changes induced in the distribution of heteroatoms at the polymer surfaces. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1408–1416, 2004     

Crystal‐Field and Covalency Effects in Uranates: An X‐ray Spectroscopic Study

The electronic structure of U^V‐ and U^VI‐containing uranates NaUO₃ and Pb₃UO₆ was studied by using an advanced technique, namely X‐ray absorption spectroscopy (XAS) in high‐energy‐resolution fluorescence‐detection (HERFD) mode. Due to a significant reduction in core–hole lifetime broadening, the crystal‐field splittings of the 5f shell were probed directly in HERFD‐XAS spectra collected at the U 3d edge, which is not possible by using conventional XAS. In addition, the charge‐transfer satellites that result from U 5f–O 2p hybridization were clearly resolved. The crystal‐field parameters, 5f occupancy, and degree of covalency of the chemical bonding in these uranates were estimated by using the Anderson impurity model by calculating the U 3d HERFD‐XAS, conventional XAS, core‐to‐core (U 4f–3d transitions) resonant inelastic X‐ray scattering (RIXS), and U 4f X‐ray photoelectron spectra. The crystal field was found to be strong in these systems and the 5f occupancy was determined to be 1.32 and 0.84 electrons in the ground state for NaUO₃ and Pb₃UO₆, respectively, which indicates a significant covalent character for these compounds.     

Anodic silver (II) oxides investigated by combined electrochemistry,ex situ XPS and in situ X‐ray absorption spectroscopy

Silver (II) oxide layers (AgO) were prepared by anodic oxidation of pre‐oxidized, Ag₂O‐covered silver electrodes in 1 M NaOH (pH 13.8). The oxidized electrodes were investigated using a combination of electrochemical techniques, ex situ X‐ray photoelectron spectroscopy (XPS) and in situ surface‐sensitive grazing incidence X‐ray absorption spectroscopy (EXAFS) under full potential control. The application of these different techniques leads to a detailed, consistent picture of the anodic silver (II) oxide layer formation. The experiments have shown that the chemical composition of the AgO layer varies significantly with oxidation potential, revealing a decreasing oxygen deficiency with increasing anodization potential and oxidation time. XPS as well as EXAFS experiments support the interpretation of the oxide as a mixed valence Ag ⁺ Ag^{3 +} O₂ with different contributions of Ag ⁺ and Ag^{3 +} species, depending on potential and anodization time. Copyright © 2009 John Wiley & Sons, Ltd.     

Aerosol damage to a microchannel plate analysed by X‐ray photoelectron spectromicroscopy

Localised corrosion on a microchannel plate has been studied using X‐ray photoelectron spectromicroscopy. Curve fitting to the spectra at each pixel in the image data set reveals the presence of sodium and carbonate species at the corrosion sites, which optical microscopy suggests originated as droplets. It is proposed that aerosol contamination of the alkali enriched microchannel plate during removal of particulate material using a stream of compressed gas was responsible for the initiation of corrosion. Copyright © 2006 John Wiley & Sons, Ltd.     

(E)‐Methyl 2‐anilinomethylene‐3‐oxobutanoate: X‐ray and density functional theory studies

Molecules of the title compound, C₁₂H₁₃NO₃, are not planar and are stabilized by electrostatic interactions, as the dipole moment of the molecule is 3.76 D. They are also stabilized by intramolecular hydrogen bonds of N...O and C...O types, and by a complicated network of weak intermolecular hydrogen bonds of the C...O type. This paper also reports the theoretical investigation of the hydrogen bonding and electronic structure of the title compound using natural bond orbital (NBO) analysis.