| 1. |
- Ottosson, Niklas, 1981-
(författare)
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Aqueous Solutions as seen through an Electron Spectrometer : Surface Structure, Hydration Motifs and Ultrafast Charge Delocalization Dynamics
- 2011
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In spite of their high abundance and importance, aqueous systems are enigmatic on the microscopic scale. In order to obtain information about their geometrical and electronic structure, simple aqueous solutions have been studied experimentally by photo- and Auger electron spectroscopy using the novel liquid micro-jet technique in conjunction with synchrotron radiation. The thesis is thematically divided into three parts. In the first part we utilize the surface sensitivity of photoelectron spectroscopy to probe the distributions of solutes near the water surface. In agreement with recent theoretical predictions we find that large polarizable anions, such as I- and ClO4-, display enhanced surface propensities compared to smaller rigid ions. Surface effects arising from ion-ion interactions at higher electrolyte concentrations and as function of pH are investigated. Studies of linear mono-carboxylic acids and benzoic acid show that the neutral molecular forms of such weak acids are better stabilized at the water surface than their respective conjugate base forms. The second part examines what type of information core-electron spectra can yield about the chemical state and hydration structure of small organic molecules in water. We demonstrate that the method is sensitive to the protonation state of titratable functional groups and that core-level lineshapes are dependent on local water hydration configurations. Using a combination of photoelectron and X-ray absorption spectroscopy we also show that the electronic re-arrangement upon hydrolysis of aldehydes yields characteristic fingerprints in core-level spectra. In the last part of this thesis we study ultrafast charge delocalization dynamics in aqueous solutions using resonant and off-resonant Auger spectroscopy. Intermolecular Coulombic decay (ICD) is found to occur in a number of core-excited solutions where excess energy is transferred between the solvent and the solute. The rate of ultrafast electron delocalization between hydrogen bonded water molecules upon oxygen 1s resonant core-excitation is found to decrease upon solvation of inorganic ions. The presented work is illustrative of how core-level photoelectron spectroscopy can be valuable in the study of fundamental phenomena in aqueous solutions.
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| 2. |
- Zhang, Chaofan
(författare)
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Multicomponent Clusters/Nanoparticles : An Investigation of Electronic and Geometric Properties by Photoelectron Spectroscopy
- 2013
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Clusters/nanoparticles are aggregates of a “small” number of building blocks, atoms or molecules, ranging from two up to millions of atoms. Two main groups of clusters have been studied using photoelectron spectroscopy based on synchrotron radiation. They are dry/wet alkali-halide clusters, including pure water clusters, and metal-based nanoparticles.For the dry alkali halide clusters, analysis of the data and theoretical modeling has allowed us insights into the local electronic properties at nanoscale: a change of polarizability of ions in the alkali-halide clusters due to the varying environment has been suggested. The study of the wet salt clusters shows that the alkali-halides are already solvated at the nanoscale reached by water clusters doped with salt vapor.The photoelectron angular distribution of water cluster shows lower anisotropy parameters as compared to the separate monomers. A model based on intracluster scattering has been built to partly explain the reduction.In the last part of the thesis, metal-based multi-component nanoparticles have been produced by self-assembly processes using reactive magnetron sputtering. Depending on the specific metal element, oxidation processes have been applied before or after the aggregation. Clearly radial distributions such as core-shell and “sandwich-like” structures have unambiguously determined by photoelectron spectroscopy.
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| 3. |
- Zhang, Teng
(författare)
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Synchrotron radiation study of free and adsorbed organic molecules
- 2016
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In this licentiate thesis, organic molecules, namely Cobalt Phthalocyanine (CoPc) and Biphenylene, have been studied by means of synchrotron radiation-based spectroscopic methods (Photoemission Spectroscopy (PES) and X-ray Absorption Spectroscopy (XAS) in combination with Density Functional Theory (DFT) calculations.Paper I is a combined experimental and theoretical investigation of electronic structure of CoPc. addressing the atomic character of the Highest Occupied Molecular Orbital (HOMO) and the electronic configuration of the molecular ground state. Both these aspects are still under discussion since different experimental and theoretical studies have given controversial results. Previous works have indicated the CoPc ground state to either be described by the 2A1g or 2Eg, or by a mix of the two electronic configurations. Regrading the debated the atomic character of the HOMO of CoPc, it has been suggested to be either metal 3d-like and localized on the central Co atom or originating in the organic ligand of the molecule. In this thesis the valence photoemission results for CoPc in gas phase and as adsorbed films on Au(111) together with the DFT simulations, consistently indicate that the HOMO is derived only by the organic ligand, with mainly contribution from the carbon atoms with no metal character. Moreover, the good agreement between the experimental and theoretical results, confirms that the ground state of CoPc is correctly described by the 2A1g configuration.In Paper II, PES and XAS have been used to investigate the occupied and empty density of states of biphenylene films of different thicknesses, deposited onto a Cu(111) crystal. The results have been compared to previous gas phase spectra and single molecule Density Functional Theory (DFT) calculations to get insights into the possible modification of the molecular electronic structure in the film induced by the adsorption on a surface. Furthermore, XAS measurements allowed the characterizion of the variation of the molecular arrangement with the film thickness and helped to clarify the substrate-molecule interaction.
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| 4. |
- Svensson, Daniel
(författare)
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Experimental methods to determine model parameters for failure modes of CFRP
- 2013
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The focus of this thesis is to develop methods to predict the damage response of Carbon Fibre Reinforced Polymers (CFRP). In the pursuit of reducing the manufacturing cost and weight of CFRP components, it is crucial to enable modelling of the non-linear response associated with various failure modes. Two failure modes are considered in this thesis: fibre compressive failure and interlaminar delamination. Multidirectional laminated composites are commonly used when a low weight is desired due to their high specific strength and stiffness. In a carbon/epoxy composite, almost exclusively the fibres carry the load. However, along the fibre direction, the compressive strength is considerably lower than the tensile strength. With the same reasoning, the transverse strength is considerably lower than the in-plane strength. This makes delamination and fibre compressive failure two of the major concerns in structural design. Moreover, the presence of delaminations severely reduces the compressive strength of a laminate. This can cause catastrophic failure of the structure. In Paper A, we suggest a test method for determining fracture properties associated with fibre compressive failure. A modified compact compression specimen is designed for this purpose and compressive failure takes place in a region consisting exclusively of fibres oriented parallel to the loading direction. The evaluation method is based on a generalized J-integral and full field measurements of the strain field on the surface of the specimen. Thus, the method is not restricted to small damage zones. Paper B focuses on measuring cohesive laws for delamination in pure mode loading. The cohesive laws in mode I and mode II are measured with the DCB- and ENF-specimen, respectively. With a method based on the J-integral, the energy release rate associated with the crack tip separation is measured directly. From this, the cohesive laws are derived. It is concluded that the nonlinear response at the crack tip is crucial in the evaluation of the mode II fracture energy.
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| 5. |
- Carlegrim, Elin, 1979-
(författare)
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Preparation and characterization of an organic-based magnet
- 2007
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In the growing field of spintronics there is a strong need for development of flexible lightweight semi-conducting magnets. Molecular organic-based magnets are attractive candidates since it is possible to tune their properties by organic chemistry, making them so-called “designer magnets”. Vanadium tetracyanoethylene, V(TCNE)x, is particularly interesting since it is a semiconductor with Curie temperature above room temperature (TC~400 K). The main problem with these organic-based magnets is that they are extremely air sensitive. This thesis reports on the frontier electronic structure of the V(TCNE)x by characterization with photoelectron spectroscopy (PES) and near edge x-ray absorption fine structure (NEXAFS) spectroscopy. It also presents a new and more flexible preparation method of this class of organic-based thin film magnets. The result shows improved air stability of the V(TCNE)x prepared with this method as compared to V(TCNE)x prepared by hitherto used methods.
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| 6. |
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