1s Absorption Research Articles

From the Free Ligand to the Transition Metal Complex: FeEDTA- Formation Seen at Ligand K-Edges.

Chelating agents are an integral part of transition metal complex chemistry with broad biological and industrial relevance. The hexadentate chelating agent ethylenediaminetetraacetic acid (EDTA) has the capability to bind to metal ions at its two nitrogen and four of its carboxylate oxygen sites. We use resonant inelastic X-ray scattering at the 1s absorption edge of the aforementioned elements in EDTA and the iron(III)-EDTA complex to investigate the impact of the metal–ligand bond formation on the electronic structure of EDTA. Frontier orbital distortions, occupation changes, and energy shifts through metal–ligand bond formation are probed through distinct spectroscopic signatures.

Positional and Conformational Isomerism in Hydroxybenzoic Acid: A Core-Level Study and Comparison with Phenol and Benzoic Acid.

Three positional isomers of hydroxybenzoic acid, as well as phenol and benzoic acid, were studied using core-level photoemission and X-ray absorption spectroscopies, supported by quantum chemical calculations. While 2-hydroxybenzoic (salicylic) acid exists as a single conformer with an internal hydrogen bond, 3- and 4-hydroxybenzoic acids are mixtures of multiple conformers. The effects due to isomerism are clearly seen in the C 1s and O 1s photoelectron spectra, whereas the conformational effects on the binding energies are less pronounced. The O 1s photoelectron spectrum of salicylic acid is significantly different from that of the other two isomers, providing a signature of the hydrogen bond. In contrast, the oxygen K edge X-ray absorption spectra of the three hydroxybenzoic acids show only minor differences. The salicylic acid absorption spectrum at the carbon K edge shows a more resolved vibrational structure than the spectra of the other molecules, which can be explained in part by the existence of a single conformer. Our theoretical study of vibrational excitations in the lowest C 1s absorption bands of salicylic and 4-hydroxybenzoic acids indicates that the observed structure can be assigned to 0-0 lines of various electronic transitions since most of the totally symmetric vibrational modes with sufficiently large frequencies to be resolved are predicted to be inactive. Significant sensitivity of the C 1s excitations in 3-hydroxybenzoic acid to rotational conformerism was predicted but not observed due to spectral crowding.

From synchrotrons for XFELs: the soft x-ray near-edge spectrum of the ESCA molecule

A predictive understanding of soft x-ray near-edge absorption spectra of small molecules is an enduring theoretical challenge and of current interest for x-ray probes of molecular dynamics. We report the experimental absorption spectrum for the electron spectroscopy for chemical analysis (ESCA) molecule (ethyl trifluoroacetate) near the carbon 1s absorption edge between 285–300 eV. The ESCA molecule with four chemically distinct carbon sites has previously served as a theoretical benchmark for photoelectron spectra and now for photoabsorption spectra. We report a simple edge-specific approach for systematically expanding standard basis sets to properly describe diffuse Rydberg orbitals and the importance of triple excitations in equation-of-motion coupled-cluster calculations of the energy interval between valence and Rydberg excitations.

Hierarchy-induced X-ray linear dichroism in cortical bone

The high-resolution X-ray absorption spectra of rat tibia cortex have been measured for two different orientations of the bone long axis in respect to the electric field vector of linear polarized synchrotron radiation. Our measurements performed near the Ca 2p and O 1s absorption edges have revealed the substantial element-specific orientation dependence of the X-ray absorption coefficient. Strong changes in intensity of core-to-valence transitions are detected near the Ca L2,3 absorption edges, whereas minor changes occur near the O K absorption edge. The specific behavior is attributed to the emergent properties of X-ray linear dichroism in cortex. This optical phenomenon is assigned with relationship between the chemical Ca–O bonds in bone and hierarchical organization of the skeleton. The hierarchy-induced X-ray linear dichroism is discussed in the framework of the 3D superlattice model and Wolff paradigm. Prospects for using this phenomenon for medical diagnosis are also being discussed.

Exploring ultra-fast charge transfer and vibronic coupling with N 1s RIXS maps of an aromatic molecule coupled to a semiconductor.

We present for the first time two-dimensional resonant inelastic x-ray scattering (RIXS) maps of multilayer and monolayer bi-isonicotinic acid adsorbed on the rutile TiO2(110) single crystal surface. This enables the elastic channel to be followed over the lowest unoccupied molecular orbitals resonantly excited at the N 1s absorption edge. The data also reveal ultra-fast intramolecular vibronic coupling, particularly during excitation into the lowest unoccupied molecular orbital-derived resonance. Both elastic scattering and the vibronic coupling loss features are expected to contain the channel in which the originally excited electron is directly involved in the core-hole decay process. This allows RIXS data for a molecule coupled to a wide bandgap semiconductor to be considered in the same way as the core-hole clock implementation of resonant photoemission spectroscopy (RPES). However, contrary to RPES measurements, we find no evidence for the depletion of the participator channel under the conditions of ultra-fast charge transfer from the molecule to the substrate densities of states, on the time scale of the core-hole lifetime. These results suggest that the radiative core-hole decay processes in RIXS are not significantly modified by charge transfer on the femtosecond time scale in this system.

Contrast enhancement of biological nanoporous materials with zinc oxide infiltration for electron and X-ray nanoscale microscopy

We show that using infiltration of ZnO metal oxide can be useful for high resolution imaging of biological samples in electron and X-ray microscopy. The method is compatible with standard fixation techniques that leave the sample dry, such as finishing with super critical CO2 drying, or simple vacuum drying up to 95 °C. We demonstrate this technique can be applied on tooth and brain tissue samples. We also show that high resolution X-ray tomography can be performed on biological systems using Zn K edge (1s) absorption to enhance internal structures, and obtained the first nanoscale 10 KeV X-ray absorption images of the interior regions of a tooth.

Photoelectron angular distribution from free SiO2 nanoparticles as a probe of elastic electron scattering.

In order to gain quantitative information on the surface composition of nanoparticles from X-ray photoelectron spectroscopy, a detailed understanding of photoelectron transport phenomena in these samples is needed. Theoretical results on the elastic and inelastic scattering have been reported, but a rigorous experimental verification is lacking. We report in this work on the photoelectron angular distribution from free SiO2 nanoparticles (d = 122 ± 9 nm) after ionization by soft X-rays above the Si 2p and O 1s absorption edges, which gives insight into the relative importance of elastic and inelastic scattering channels in the sample particles. The photoelectron angular anisotropy is found to be lower for photoemission from SiO2 nanoparticles than that expected from the theoretical values for the isolated Si and O atoms in the photoelectron kinetic energy range 20-380 eV. The reduced angular anisotropy is explained by elastic scattering of the outgoing photoelectrons from neighboring atoms, smearing out the atomic distribution. Photoelectron angular distributions yield detailed information on photoelectron elastic scattering processes allowing for a quantification of the number of elastic scattering events the photoelectrons have undergone prior to leaving the sample. The interpretation of the experimental photoelectron angular distributions is complemented by Monte Carlo simulations, which take inelastic and elastic photoelectron scattering into account using theoretical values for the scattering cross sections. The results of the simulations reproduce the experimental photoelectron angular distributions and provide further support for the assignment that elastic and inelastic electron scattering processes need to be considered.

A spectroscopic comparison of IGZO thin films and the parent In2O3, Ga2O3, and ZnO single crystals

We use resonant photoelectron spectroscopy at the Zn 2p, Ga 2p, In 3d, and O 1s absorption edges to report on the electronic properties of indium–gallium–zinc-oxide thin films. We also compare the data with the respective data of the corresponding single crystals In2O3, Ga2O3, and ZnO. We focus on the elemental composition and, in particular, find no evidence for oxygen deficiency. The In, Ga, and Zn absorption data at resonance can be used to analyze the conduction band states in detail. We deduce that a configuration interaction between d10s0 and d9s1states is of importance. We provided a novel mechanism in which configuration interaction induced gap states create both, extended unoccupied states around EF as well as localized occupied states within the gap.

Electron Spectroscopy of Single Quantum Objects To Directly Correlate the Local Structure to Their Electronic Transport and Optical Properties.

Physical property of a single quantum object is governed by its precise atomic arrangement. The direct correlation of localized physical properties with the atomic structures has been therefore strongly desired but still limited in the theoretical studies. Here, we have successfully examined the localized electronic properties of individual carbon nanotubes by means of high-resolution electron energy-loss spectroscopy combined with high-resolution transmission electron microscopy. Well-separated sharp peaks at the carbon K(1s) absorption edge and in the valence-loss spectra are obtained from a single freestanding carbon nanotube with the local chiral index and unambiguously identified as the transitions between the van Hove singularities. The spectra features clearly vary upon the different areas even in the individual carbon nanotube. Variations in interband transitions, plasmonic behaviors, and unoccupied electronic structures are clearly attributed to the local irregular atomic arrangement such as topological defect and/or elastic bond stretching.

Femtosecond Electron Delocalization in Polymer:Fullerene Blend Films

SynopsisUltrafast electron dynamics in the low-femtosecond regime was evaluated for a low band-gap polymer and its blend with fullerene by resonant Auger spectroscopy. Remarkable changes developed by tuning the photon energy along the sulfur and silicon 1s absorption edges. The effect of thermal annealing and molecular orientation on the charge transfer delocalization times were probed and correlated with solar cells performance.

Single molecular spectroscopy: identification of individual fullerene molecules.

We report the molecule-by-molecule spectroscopy of individual fullerenes by means of electron spectroscopy based on scanning transmission electron microscopy. Electron energy-loss fine structure analysis of carbon 1s absorption spectra is used to discriminate carbon allotropes with known symmetries. C(60) and C(70) molecules randomly stored inside carbon nanotubes are successfully identified at a single-molecular basis. We show that a single molecule impurity is detectable, allowing the recognition of an unexpected contaminant molecule with a different symmetry. Molecules inside carbon nanotubes thus preserve their intact molecular symmetry. In contrast, molecules anchored at or sandwiched between atomic BN layers show spectral modifications possibly due to a largely degraded structural symmetry. Moreover, by comparing the spectrum from a single C(60) molecule and its molecular crystal, we find hints of the influence of solid-state effects on its electronic structure.

Invited: Advances in Structural Characterization of PEM Fuel Cell Catalyst Layers By Soft X-Ray Scanning Transmission Microscopy

Proton exchange membrane fuel cells (PEMFCs) are among the most attractive alternative energy sources for automotive application due to their high power density, high efficiency, and potential to significantly reduce adverse environmental impact. However, high material costs and durability issues remain major challenges for large scale commercialization [1, 2]. The catalyst coated membrane (CCM), as a main component in PEMFCs, that employs expensive Pt based porous electrode layers responsible for the generation of pathways for reactant transport enabling efficient electron and proton conductivity and managing product water removal. Improved understanding of the relationship between material properties, electrode structure and overall fuel cell performance is essential for material and process down-selection in order to establish the most cost effective PEMFC manufacturing process. For that reason, the development of new, non destructive characterization methods to allow evaluation of catalyst layer composition and microstructure with high spatial resolution and individual component mapping is needed. In recent years, a novel synchrotron based technique: soft X-ray scanning transmission microscopy (STXM) has emerged and extended the number of standard available microscopic characterization tools and significantly improving our understanding of how materials are distributed from micro to nano-scales in fuel cell electrodes. STXM is able to image a fuel cell catalyst layer and differentiate each chemically specific material component due to its near edge X-ray specific absorption (NEXAFS) signature [3-11]. The spatial resolution of this method is 30 nm. We have developed several STXM applications to characterize a) materials in the dry CCM in 2D cross sections, b) in 3D, and c) while applying environmental changes in 2D. Using two-energy mapping at F 1s and C 1s edges, a 2D material reconstruction methodology for catalyst layer micro-structural characterization and ionomer mapping was developed [7]. Both conventional and nanostructured thin film (NSTF) based catalyst layers are being investigated [9, 10]. Applying a tomographic approach, a STXM spectro-tomography method was established and proven to provide a 3D reconstruction of the cathode catalyst layer with spatially resolved carbon and ionomer species [8]. Due to its ability to spectroscopically differentiate gas, liquid and solid water using the O 1s absorption edge, STXM is being applied to study hydrated CCMs [7]. An environmental wet cell for in situSTXM studies of CCM components under controllable temperature and relative humidity conditions has been developed and used to map all three phases of water in the electrode under various conditions including those relevant to cold start. In this paper and the coming talk, we will review progress in development of STXM methodology for characterization of catalyst layer structures. Efforts in deriving parameters to aid structure-properties-performance correlations will be discussed.STXM measurements are carried out at the Canadian Light Source and at the Advanced Light source.

Electronic structure, molecular orientation, charge transfer dynamics and solar cells performance in donor/acceptor copolymers and fullerene: Experimental and theoretical approaches

By combining experimental and theoretical approaches, the electronic structure, molecular orientation, charge transfer dynamics and solar cell performance in donor/acceptor copolymer poly[2,7-(9,9-bis(2-ethylhexyl)-dibenzosilole)-alt-4,7-bis(thiophen-2-yl)benzo-2,1,3-thiadiazole] (PSiF-DBT) films and blended with 6,6.-phenyl-C 61-butyric acid methyl ester (PSiF-DBT:PCBM) were investigated. Good agreement between experimental and theoretical PSiF-DBT UV-Vis absorption spectrum is observed and the main molecular orbitals contributing to the spectrum were determined using DFT single point calculations. Non-coplanar configuration was determined by geometric optimization calculation in isolated PSiF-DBT pentamer and corroborated by angular variation of the sulphur 1s near-edge X-ray absorption fine structure (NEXAFS) spectra. Edge-on and plane-on molecular orientations were obtained for thiophene and benzothiadiazole units, respectively. A power conversion efficiency up to 1.58%, open circuit voltage of 0.51 V, short circuit current of 8.71 mA/cm2 and a fill factor of 35% was obtained using blended PSiF-DBT:PCBM as active layer in a bulk heterojunction solar cell. Ultrafast electron dynamics in the low-femtosecond regime was evaluated by resonant Auger spectroscopy using the core-hole clock methodology around sulphur 1s absorption edge. Electron delocalization times for PSiF-DBT and PSiF-DBT:PCBM polymeric films were derived for selected excitation energies corresponding to the main transitions in the sulphur 1s NEXAFS spectra. The mixture of PSiF-DBT with PCBM improves the charge transfer process involving the π* molecular orbital of the thiophene units.

Temperature-dependent photoluminescence Stokes shift in PbS quantum dots

Following the long dominance of CdSe quantum dots as the paradigm semiconductor nanocrystals for investigating of strong quantum confinement phenomena, attention is paid to the lead chalcogenide quantum dots which possess a level of carrier confinement unachievable in quantum dots of other materials. However, the energy level structure of the lowest 1S–1S exciton in these quantum dots is not defined well. Here, we report on the experimental investigation of absorption and photoluminescence of PbS quantum dots with a mean radius of 2.4nm and show that the 1S–1S absorption and photoluminescence band maxima obey different temperature dependences. The temperature decrease leads to the increase of the Stokes shift. The results are in qualitative agreement with the assumption that different inherent exciton states within the split 1S–1S exciton state are responsible for the absorption and emission of light by PbS quantum dots.

Accurate and Facile Determination of the Index of Refraction of Organic Thin Films Near the Carbon1sAbsorption Edge

A practical and accurate method to obtain the index of refraction, especially the decrement δ, across the carbon 1s absorption edge is demonstrated. The combination of absorption spectra scaled to the Henke atomic scattering factor database, the use of the doubly subtractive Kramers-Kronig relations, and high precision specular reflectivity measurements from thin films allow the notoriously difficult-to-measure δ to be determined with high accuracy. No independent knowledge of the film thickness or density is required. High confidence interpolation between relatively sparse measurements of δ across an absorption edge is achieved. Accurate optical constants determined by this method are expected to greatly improve the simulation and interpretation of resonant soft x-ray scattering and reflectivity data. The method is demonstrated using poly(methyl methacrylate) and should be extendable to all organic materials.

Femtosecond Electron Delocalization in Poly(thiophene) Probed by Resonant Auger Spectroscopy

Ultrafast electron dynamics in the low-femtosecond regime was evaluated for poly(thiophene) by resonant Auger spectroscopy using the core-hole clock method. Sulfur KL2,3L2,3 Auger decay spectra were measured as a function of the photon energy. Remarkable changes developed by tuning the photon energy along the sulfur 1s absorption edge, depending on the nature of the intermediate core excited states. Features characteristics of the Auger Resonant Raman effect were observed. Competition between core hole decay and delocalization of the photoexcited electron was monitored. Branching ratios of Raman (spectator) and normal Auger channels were calculated and electron delocalization times derived.

Design of solar cell materials via soft X-ray spectroscopy

This overview illustrates how spectroscopy with soft X-rays can assist the development of new materials and new designs for solar cells. The starting point is the general layout of a solar cell, which consists of a light absorber sandwiched between an electron donor and an electron acceptor. There are four relevant energy levels that can be measured with a combination of X-ray absorption spectroscopy and photoelectron spectroscopy, as illustrated for an organic dye as absorber attached to a p-doped diamond film as donor. Systematic measurements of organometallic dyes (phthalocyanines and porphyrins) as a function of the metal atom are presented for the metal 2p and N 1s absorption edges. In combination with density functional theory one can discern trends that are useful for tailoring absorber molecules. A customized porphyrin molecule is investigated that combines an absorber with a donor and a linker to an oxide acceptor. The bridge to device fabrication is crossed by correlating spectroscopic features with the photocurrent in hematite photoanodes for water splitting. For speeding up the development of new materials and designs of solar cells a feedback loop between spectroscopy, theory, synthesis and device fabrication is envisioned.

Modeling Near-Edge Fine Structure X-ray Spectra of the Manganese Catalytic Site for Water Oxidation in Photosystem II

The Mn 1s near-edge absorption fine structure (NEXAFS) has been computed by means of transition-state gradient-corrected density functional theory (DFT) on four Mn(4)Ca clusters modeling the successive S(0) to S(3) steps of the oxygen-evolving complex (OEC) in photosystem II (PSII). The model clusters were obtained from a previous theoretical study where they were determined by energy minimization. They are composed of Mn(III) and Mn(IV) atoms, progressing from Mn(III)(3)Mn(IV) for S(0) to Mn(III)(2)Mn(IV)(2) for S(1) to Mn(III)Mn(IV)(3) for S(2) to Mn(IV)(4) for S(3), implying an Mn-centered oxidation during each step of the photosynthetic oxygen evolution. The DFT simulations of the Mn 1s absorption edge reproduce the experimentally measured curves quite well. By the half-height method, the theoretical IPEs are shifted by 0.93 eV for the S(0) → S(1) transition, by 1.43 eV for the S(1) → S(2) transition, and by 0.63 eV for the S(2) → S(3) transition. The inflection point energy (IPE) shifts depend strongly on the method used to determine them, and the most interesting result is that the present clusters reproduce the shift in the S(2) → S(3) transition obtained by both the half-height and second-derivative methods, thus giving strong support to the previously suggested structures and assignments.

Experimentally observed orientation of C60F18 molecules on the nickel single crystal (100) surface

The angular dependence of near edge X-ray absorption fine structure (NEXAFS) spectra has been obtained in the vicinity of carbon and fluorine 1s absorption edges in a monolayer film of polar fullerene fluoride (C60F18) molecules on a Ni(100) substrate. The fine structure of the spectra has been identified according to experimental data via calculations based on the density functional theory, and the angular dependence of the spectra has been explained. The orientations of structural molecular fragments are determined from the angular dependence of the NEXAFS spectra. It is demonstrated that the electric dipole moment of a C60F18 molecule is oriented along the normal to the substrate surface with an accuracy of 5°.

Optical properties of novel PbS and PbSe quantum-dot-doped alumino-alkali-silicate glasses

Lead sulfide PbS and lead selenide PbSe quantum dots (QDs) were synthesized in novel alumino-alkali-silicate glass. The synthesis of the nanocrystals was stabilized by introduction of two alkaline components. The presence of crystalline phase was confirmed by X-ray diffraction analysis, transmission electron microscopy and optical spectroscopy. For PbS (PbSe) QD-doped glass, the position of the 1S–1S excitonic absorption peak can be managed in the spectral range of 1.5–2.1μm (for PbS) or 1.8–2.2μm (for PbSe) by appropriate heat‐treatment mode. The corresponding QD average diameter was found to be 5.8–9.7nm (for PbS) and 7.5–9.5nm (for PbSe). The influence of the secondary heat-treatment at the temperatures of 490–525°C on the PbS QD growth in the glass matrix initially treated at 480°C was studied in details. The photoluminescence of the PbS-QD-doped glass was observed, it was referred to the radiative recombination of the excitons from the 1S–1S state. The possibility to obtaining narrow 1S–1S absorption lines at the wavelengths longer than 2μm is discussed.