Interpretation of experimental N K NEXAFS of azide, 1,2,3-triazole and terpyridyl groups by DFT spectrum simulations

Experimental N K-edge NEXAFS data of surface immobilized azide, 1,2,3-triazole and terpyridyl groups are interpreted with the help of DFT spectrum simulations. Assignments of π* resonances in experimental N K-edge NEXAFS spectra to nitrogen atoms within these functional groups have been made. The azide was immobilized on gold as the head group of a thiol SAM, 1,2,3-triazole was formed on this SAM by click reaction and terpyridyl groups were introduced as substituents of the acetylene used for the click reaction. For azide-terminated molecules, DFT spectrum simulations are found to be useful to find measurement conditions delivering experimental N K-edge NEXAFS data with negligible X-ray damage. The 1,2,3-triazole group is found to be rather stable under X-ray irradiation.     

X‐ray spectromicroscopy in soil and environmental sciences

X‐ray microscopy is capable of imaging particles in the nanometer size range directly with sub‐micrometer spatial resolution and can be combined with high spectral resolution for spectromicroscopy studies. Two types of microscopes are common in X‐ray microscopy: the transmission X‐ray microscope and the scanning transmission X‐ray microscope; their set‐ups are explained in this paper. While the former takes high‐resolution images from an object with exposure times of seconds or faster, the latter is very well suited as an analytical instrument for spectromicroscopy. The morphology of clusters or particles from soil and sediment samples has been visualized using a transmission X‐ray microscope. Images are shown from a cryo‐tomography experiment based on X‐ray microscopy images to obtain information about the three‐dimensional structure of clusters of humic substances. The analysis of a stack of images taken with a scanning transmission X‐ray microscope to combine morphology and chemistry within a soil sample is shown. X‐ray fluorescence is a method ideally applicable to the study of elemental distributions and binding states of elements even on a trace level using X‐ray energies above 1 keV.     

Formation of sharp metal-organic semiconductor interfaces: Ag and Sn on CuPc

A detailed investigation of the chemistry and electronic structure during the formation of the interfaces between thin films of the archetypal organic molecular semiconductor copper phthalocyanine (CuPc) and Ag or Sn deposited on it was performed using photoemission and near-edge X-ray absorption spectroscopies with synchrotron light. Our study demonstrates the formation of sharp, abrupt interfaces, a behavior which is of particular importance for applications in organic devices. Moreover, for Ag on CuPc we demonstrate that this interface is free from any reaction, whereas there is slight interface reaction for Sn/CuPc.     

In-situ measurement of molecular orientation of the pentacene ultrathin films grown on SiO2 substrates

Molecular orientations of pentacene ultrathin films grown on SiO₂ substrates were studied without the influence of the atmosphere by vacuum atomic force microscopy (V-AFM) and near edge X-ray absorption fine structure (NEXAFS). The experimental processes from deposition of pentacene to characterization of films were performed under vacuum condition without exposure to the atmosphere. V-AFM and NEXAFS measurements showed that pentacene molecules tend to grow on SiO₂ surface with their molecular long axes perpendicular to the substrate surfaces (standing-mode) irrespective of preparation procedure of SiO₂ substrate.     

Simulation of NEXAFS spectra of a photo-reactive copolymer with considerably large monomer units: An ab initio molecular orbital study

We performed the simulation of near edge X-ray absorption fine structure (NEXAFS) spectra of a photo-reactive copolymer with considerably large monomer units by ab initio molecular orbital calculation, in order to explain the spectral change induced by irradiation of the linearly polarized near ultra-violet (LPNUV) light. The “building block approach” is applied for the theoretical calculation to calculate the core-excited states of the polymer with such large monomer units; the monomer unit is divided into subunits, whose core-excited states are calculated individually, and the results are summed up to simulate the spectra of the polymer. With the result of the simulation, the peaks in the observed spectra were assigned. The spectral change after the LPNUV-irradiation is attributed to the change in the electronic structure caused by the breakdown of the π-conjugation system of chalconyl group after photo-dimerization.     

Chemical states of nitrogen in ZnO studied by near-edge X-ray absorption fine structure and core-level photoemission spectroscopies

Interaction of low-energy nitrogen ions with ZnO surface has been studied by photoemission spectroscopy (PES) around N 1s core-level and near-edge X-ray absorption fine structure (NEXAFS) around N K-edge. Nitrogen can break Zn-O bonds at the surface and form N-O, Zn-N or Zn-N-O bonds, characterised by specific chemical shifts in PES or absorption peaks in NEXAFS. A distinctive signal from molecular nitrogen has also been observed in ion-bombarded samples in both NEXAFS and PES.     

Influence of crystal structure,ligand environment and morphology on Co L‐edge XAS spectral characteristics in cobalt compounds

The electronic structure of a material plays an important role in its functionality for different applications which can be probed using synchrotron‐based spectroscopy techniques. Here, various cobalt‐based compounds, differing in crystal structure, ligands surrounding the central metal ion and morphology, have been studied by soft X‐ray absorption spectroscopy (XAS) at the Co L‐edge in order to measure the effect of these parameters on the electronic structure. A careful qualitative analysis of the spectral branching ratio and relative intensities of the L₃ and L₂ peaks provide useful insight into the electronic properties of compounds such as CoO/Co(OH)₂, CoCl₂.6H₂O/CoF₂.4H₂O, CoCl₂/CoF₂, Co₃O₄ (bulk/nano/micro). For further detailed analysis of the XAS spectra, quantitative analysis has been performed by fitting the spectral profile with simulated spectra for a number of cobalt compounds using crystal field atomic multiplet calculations.     

The local structure of SO2 and SO3 on Ni(1 1 1)

The normal incidence X-ray standing wave (NIXSW) technique, supported by X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure (NEXAFS), has been used to determine the local adsorption geometry of SO₂ and SO₃ on Ni(1 1 1). Chemical-state specific NIXSW data for coadsorbed SO₃ and S, formed by the disproportionation of adsorbed SO₂ after heating from 140 K to 270 K, were obtained using S 1s photoemission detection. For adsorbed SO₂ at 140 K the new results confirm those of an earlier study [Jackson et al., Surf. Sci. 389 (1997) 223] that the molecule is located above hollow sites with its molecular plane parallel to the surface and the S and O atoms in off-atop sites; corrections to account for the non-dipole effects in the interpretation of the NIXSW monitored by S 1s and O 1s photoemission, not included in the earlier work, remove the need for any significant adsorption-induced distortion of the SO₂ in this structure. SO₃, not previously investigated, is found to occupy an off-bridge site with the C_3v axis slightly tilted relative to the surface normal and with one O atom in an off-atop site and the other two O atoms roughly between bridge and hollow sites. The O atoms are approximately 0.87 Å closer to the surface than the S atom. This general bonding orientation for SO₃ is similar to that found on Cu(1 1 1) and Cu(1 0 0) both experimentally and theoretically, although the detailed adsorption sites differ.     

Adsorption of some substituted ethylene molecules on Pt(111) at 95 K Part 1: NEXAFS, XPS and UPS studies

The present work examines the interactions of propanoic acid, acrylic acid, acrolein and methylmethacrylate (MMA) with Pt(111) at 95 K to identify the nature of the interactions on this surface. The investigations are carried out by XPS, UPS and NEXAFS on monolayer and multilayer. Theoretical molecular orbital calculations are firstly performed to determine the nature of the bonding and antibonding orbitals of these molecules. The NEXAFS results show that the condensed multilayers of acrylic acid and acrolein are almost oriented parallel to the surface when propanoic acid and MMA are randomly oriented. The monolayer formed at 95 K for all these molecules are also oriented flat on Pt(111). However two different interaction processes are observed depending on the chemical structure of the compound: acrolein and propanoic acid are physisorbed when MMA and acrylic acid are in strong interaction with the metal but with an uncertainty on the chemisorption mode between a π-bonded state or a “di-σ like” state.     

Structural, magnetic and electronic structure studies of Mn doped TiO2 thin films

We report structural, magnetic and electronic structure study of Mn doped TiO₂ thin films grown using pulsed laser deposition method. The films were characterized using X-ray diffraction (XRD), dc magnetization, X-ray magnetic circular dichroism (XMCD) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy measurements. XRD results indicate that films exhibit single phase nature with rutile structure and exclude the secondary phase related to Mn metal cluster or any oxide phase of Mn. Magnetization studies reveal that both the films (3% and 5% Mn doped TiO₂) exhibit room temperature ferromagnetism and saturation magnetization increases with increase in concentration of Mn doping. The spectral features of XMCD at Mn L_3,2 edge show that Mn²⁺ ions contribute to the ferromagnetism. NEXAFS spectra measured at O K edge show a strong hybridization between Mn, Ti 3d and O 2p orbitals. NEXAFS spectra measured at Mn and Ti L_3,2 edge show that Mn exist in +2 valence state, whereas, Ti is in +4 state in Mn doped TiO₂ films.