This thesis presents experimental studies of three different chemical reaction steps relevant for heterogeneous catalysis: dissociation, desorption, and oxidation. CO on single-crystal metal surfaces was chosen as the model systems. X-ray absorption spectroscopy (XAS) and x-ray emission spectroscopy (XES) provide information about the electronic structure, and were performed on CO/Fe to measure both a non-dissociative, and a pre-dissociative state. The measurement on the pre-dissociative state showed a π →  π* excitation, which implies a partly broken internal π bond in the molecule. Ultrafast laser-induced reactions were used to examine the dynamic properties of desorption and oxidation. Here CO/Ru and CO/O/Ru were used as model systems. Desorption of CO from a Ru surface involve both hot electrons and phonons. In the case of CO oxidation from CO/O/Ru a pronounced wavelength dependence of the branching ratio between desorption and oxidation was observed. Excitation with 400 nm showed a factor of 3-4 higher selectivity towards oxidation than 800 nm. This was attributed to coupling to transiently excited, non-thermalized electrons. Finally, by performing optical pump/x-ray probe XAS and XES changes in the electronic structure during the reaction could be followed, both for desorption and oxidation. In the CO/Ru experiment, two different transient excitation paths were observed, one leading to a precursor state, and one where CO moves into a more highly coordinated site. Using selective excitation in XES, these were shown to coexist on the surface. In the oxidation experiment, probing the reacting species located near the transition state region in an associative catalytic surface reaction was demonstrated for the very first time.

At the MAX-IV lab in Lund, there is a current goal to build a new soft X-Ray laser. The beam will be generated from a free-electron laser (FEL), which is an instrument consisting of high-speed electrons. The electrons move through alternating magnetic fields, causing the beam to become monochromatic. After the FEL, the Xrays will enter a beamline consisting of different optical components, such as mirrors, gratings and slits. This project investigated the necessary parameter values of the components, in order for the new X-Ray laser to focus the beam enough. The project consisted of a theoretical part and a simulation part. The use of so-called Kirkpatrick-Baez mirrors enables the beam to be very focused. The best focus achieved was 7.23um*10.87um for ''Pink beamline'' and the intensity at the end was 71.5%, which meant that only 30% of the rays were lost. For the monochromatic beamline, a loss of intensity is inevitable. With a pair of KBmirrors, this beam was focused to be 6.95um*9.80um. The energy spread is ranging from 6.198 eV to 0.3442 eV. The analytical calculations for the spot size matched well with the simulations. The pink beamline which was built in Ray satisfied the criterias of a spot size and intensity loss. The monochromatic beamline did fullfil the criterias of spot size and narrowing the energy spread. A loss of intensity will for this beamline be inevitable. Studying the misalignment effect showed that the components were most sensitive for vertical misalignment. The most sensitive parameters were the curvature of the mirrors.

Direct volume rendering techniques for scalar fields make use of transfer functions to map optical properties to the field; the field can subsequently be visualized through the drawing of isosurfaces in the volume spanned by the field. The utility of this approach is limited in the case of nested or clustered structures with the same isovalue and further does not easily allow for quantitative measurements of the visualized data. This report explores the use of topological structures (contour trees and Morse-Smale complexes) as an augmentation of traditional direct volume rendering and describes a fully functional implementation in the visualization software Inviwo. The implementation is evaluated through analysis of valency charge density fields in cubic MgO2 and FeO2. It is demonstrated that both contour trees and Morse-Smale complexes provide information and segmentation of initial volume data that allows for selective transfer function application (based on the segmentation), on-demand information on critical points and an overview of the scalar field through a topological representation embedded in the visualized volume. Analysis of the provided charge density fields show that contour trees generate physically irrelevant artefacts and thus are ill-suited for analysing highly symmetric data. On the other hand, the Morse-Smale complex approach is used to extract information of the bond strength of O-O contacts in MgO2 and FeO2 consistent with previous findings, as well as information on electronic charge configuration consistent with previous findings on MgO2. In the case of FeO2, the electronic configuration results are not consistent. This is speculated to be due to a combination of factors, most notably the lack of periodic boundary conditions in the implementation and the more complicated structure of FeO2.   In light of the partially accurate data analysis, as well as the added functionality and utility provided to visualization software, this approach to topology-guided visualization is considered promising and worthy of further study and/or development.

Transformation optics, a recently booming area, provides people a new approach to design optical devices for manipulating light. With transformation optics, a lot of novel optical devices are proposed, such as invisibility cloaks, optical wormholes, optical black holes, illusion devices. The present thesis is devoted to investigate transformation optics for manipulating light. Firstly, an introduction to transformation optics is given. This part includes: (1) introducing differential geometry as the mathematical preparation; (2) expressing Maxwell’s equations in an arbitrary coordinate system and introducing the concept of transformation media as the foundation stone of transformation optics; (3) discussing light from the geometry perspective as the essence of transformation optics; (4) showing how to use transformation optics to design optical devices. For our works on invisibility cloaks, we analyze the properties of arbitrary shaped invisibility cloaks, and confirm their invisibility abilities. The geometrical perturbations to cylindrical and spherical shaped cloaks are analyzed in detail. We show that the cylindrical cloak is more sensitive to the perturbation than a spherical cloak. By imposing a PEC (PMC) layer at the interior boundary of the cylindrical cloak shell for TM (TE) wave, the sensitivity can be reduced dramatically. A simplified non-magnetic cylindrical cloak is also designed. We show that the dominant zeroth order scattering term can be eliminated by employing an air gap between the cloak and the cloaked region. We propose a compensated bilayer by a folding coordinate transformation based on transformation optics. It is pointed out that complementary media, perfect negative index lens and perfect bilayer lens made of indefinite media are well unified under the scope of the transformed compensated bilayer. We demonstrate the applications of the compensated bilayer, such as perfect imaging and optical illusion. Arbitrary shaped compensated bilayers are also analyzed. Nihility media known as the media with ε =μ= 0, are generalized from transformation optics as transformation media derived from volumeless geometrical elements. The practical constructions of nihility media by metamaterials are discussed. The eigen fields in the nihility media are derived. The interactions between an external incident wave and a slab of nihility media in the free space background are analyzed. A new type of transformation media called α media is proposed for manipulating light. Light rays in the α media have a simple displacement or rotation relationship with those in another media (seed media). Such relationship is named α relationship. The α media can be designed and simplified to a certain class of diagonal anisotropic media, which are related to certain isotropic media by the α relationship. Several optical devices based on the α transformation media are designed. Invisibility cloaks obtained from the coordinate transformation approach are revisited from a different perspective. / QC 20101102

This thesis is about modelling and predicting the perceived whiteness of plain paper from the paper composition, including fluorescent whitening agents. This includes psycho-physical modelling of perceived whiteness from measurable light reflectance properties, and physical modelling of light scattering and fluorescence from the paper composition. Existing models are first tested and improvements are suggested and evaluated. The standardised and widely used CIE whiteness equation is first tested on commercial office papers with visual evaluations by different panels of observers, and improved models are validated. Simultaneous contrast effects, known to affect the appearance of coloured surfaces depending on the surrounding colour, are shown to significantly affect the perceived whiteness. A colour appearance model including simultaneous contrast effects  (CIECAM02-m2), earlier tested on coloured surfaces, is successfully applied to perceived whiteness. A recently proposed extension of the Kubelka-Munk light scattering model including fluorescence for turbid media of finite thickness is successfully tested for the first time on real papers. It is shown that the linear CIE whiteness equation fails to predict the perceived whiteness of highly white papers with distinct bluish tint. This equation is applicable only in a defined region of the colour space, a condition that is shown to be not fulfilled by many commercial office papers, although they appear white to most observers. The proposed non-linear whiteness equations give to these papers a whiteness value that correlates with their perceived whiteness, while application of the CIE whiteness equation outside its region of validity overestimates perceived whiteness. It is shown that the quantum efficiency of two different fluorescent whitening agents (FWA) in plain paper is rather constant with FWA type, FWA concentration, filler content, and fibre type. Hence, the fluorescence efficiency is essentially dependent only on the ability of the FWA to absorb light in its absorption band.  Increased FWA concentration leads accordingly to increased whiteness. However, since FWA absorbs light in the violet-blue region of the electromagnetic spectrum, the reflectance factor decreases in that region with increasing FWA amount. This violet-blue absorption tends to give a greener shade to the paper and explains most of the observed greening and whiteness saturation at larger FWA concentrations. A red-ward shift of the quantum efficiency is observed with increasing FWA concentration, but this is shown to have a negligible effect on the whiteness value. The results are directly applicable to industrial applications for better instrumental measurement of whiteness and thereby optimising the use of FWA with the goal to improve the perceived whiteness. In addition, a modular Monte Carlo simulation tool, Open PaperOpt, is developed to allow future spatial- and angle-resolved particle level light scattering simulation. / PaperOpt

This dissertation is focused on theoretical and experimental studies of optical properties of materials and multilayer structures composing liquid crystal displays (LCDs) and electrochromic (EC) devices. By applying spectroscopic ellipsometry, we have determined the optical constants of thin films of electrochromic tungsten oxide (WOx) and nickel oxide (NiOy), the films’ thickness and roughness. These films, which were obtained at spattering conditions possess high transmittance that is important for achieving good visibility and high contrast in an EC device. Another application of the general spectroscopic ellipsometry relates to the study of a photo-alignment layer of a mixture of azo-dyes SD-1 and SDA-2. We have found the optical constants of this mixture before and after illuminating it by polarized UV light. The results obtained confirm the diffusion model to explain the formation of the photo-induced order in azo-dye films. We have developed new techniques for fast characterization of twisted nematic LC cells in transmissive and reflective modes. Our techniques are based on the characteristics functions that we have introduced for determination of parameters of non-uniform birefringent media. These characteristic functions are found by simple procedures and can be utilised for simultaneous determination of retardation, its wavelength dispersion, and twist angle, as well as for solving associated optimization problems. Cholesteric LCD that possesses some unique properties, such as bistability and good selective scattering, however, has a disadvantage – relatively high driving voltage (tens of volts). The way we propose to reduce the driving voltage consists of applying a stack of thin (~1µm) LC layers. We have studied the ability of a layer of a surface stabilized ferroelectric liquid crystal coupled with several retardation plates for birefringent color generation. We have demonstrated that in order to accomplish good color characteristics and high brightness of the display, one or two retardation plates are sufficient.

Fluorescent molecules commonly shift to transient dark states, induced bylight or triggered by chemical reactions. The transient dark states can beused as probes of the local environment surrounding the fluorescent molecules,and are therefore attractive for use in biomolecular applications. Thisthesis explores the use and development of novel fluorescence spectroscopictechniques for monitoring transient dark states.This work demonstrates that kinetic information regarding photoinduced transient dark states of fluorescent molecules can be obtained from the time-averaged fluorescence intensity of fluorescent molecules subject totemporally modulated illumination. Methods based on this approach havethe advantage that the light detectors can have a low time resolution, which allows for parallelization and screening of biomolecular interactions withhigh throughput. Transient state images are presented displaying local environmental differences such as those in oxygen concentration and quencher accessibility.Analysis of the fluorescence intensity fluctuations resulting from thetransitions to and from transient dark states can be used to obtain information regarding the transition rates and occupancy of the transient darkstates. Fluorescence fluctuation analysis was used to reveal rates of protonbinding and debinding to single fluorescent molecules located close to biological membranes and protein surfaces. The results from these studies show that the proton exchange rate increases dramatically when the fluorescent molecule is close to the membrane. / QC 20100809

Soft x-ray microscopy in the water-window (λ = 2.28 nm – 4.36 nm) is based on zone-plate optics and allows high-resolution imaging of, e.g., cells and soils in their natural or near-natural environment. Three-dimensional imaging is provided via tomographic techniques, soft x-ray cryo tomography. However, soft x-ray microscopes with such capabilities have been based on large-scale synchrotron x‑ray facilities, thereby limiting their accessibility for a wider scientific community. This Thesis describes the development of the Stockholm laboratory soft x-ray microscope to three-dimensional cryo tomography and to new optics-based contrast mechanisms. The microscope relies on a methanol or nitrogen liquid-jet laser-plasma source, normal-incidence multilayer or zone-plate condenser optics, in-house fabricated zone-plate objectives, and allows operation at two wavelengths in the water-window, λ = 2.48 nm and λ = 2.48 nm. With the implementation of a new state-of-the-art normal-incidence multilayer condenser for operation at λ = 2.48 nm and a tiltable cryogenic sample stage the microscope now allows imaging of dry, wet or cryo-fixed samples. This arrangement was used for the first demonstration of laboratory soft x-ray cryo microscopy and tomography. The performance of the microscope has been demonstrated in a number of experiments described in this Thesis, including, tomographic imaging with a resolution of 140 nm, cryo microscopy and tomography of various cells and parasites, and for studies of aqueous soils and clays. The Thesis also describes the development and implementation of single-element differential-interference and Zernike phase-contrast zone-plate objectives. The enhanced contrast provided by these optics reduce exposure times or lowers the dose in samples and are of major importance for harder x-ray microscopy. The implementation of a high-resolution 50 nm compound zone-plate objective for sub-25-nm resolution imaging is also described. All experiments are supported by extensive numerical modelling for improved understanding of partially coherent image formation and stray light in soft x-ray microscopes. The models are useful tools for studying effects of zone plate optics or optical design of the microscope on image formation and quantitative accuracy in soft x-ray tomography. / QC 20110221

Illuminated metal nanoparticles (MNPs) feature collective electron oscillations (so-called localized surface plasmons or LSPs) which facilitate concentrating light-matter interactions to length scales below the diffraction limit. Part I of this book describes two applications of this confinement effect. Firstly, the use of single particles as optically active probes for scanning near-field optical microscopy is demonstrated. Secondly, fluorescence enhancement in the vicinity of a single MNP is described theoretically. This description focuses on how the particle diameter and the surrounding medium influence the enhancement. It turned out that in these two examples the optical signal levels can be improved by manipulating the spectral LSP resonance position of the particles. This finding triggered the search for a method allowing optical particle tuning. Part II of this thesis describes an approach which allows such a spectral LSP manipulation on the single-particle level. The method makes use of the optically induced reduction of metal salt complexes in solution, which leads to the deposition of thin layers of elemental metal onto single, intentionally addressed particles. The deposition process is monitored by optical LSP analysis, and thus the tuning of the optical particle properties is controlled in situ. With this technique, a manipulation of both the size and the shape of single nanoparticles was achieved. Initial experiences were gained by manipulating spherical and ellipsoidal gold particles, for which a red- and a blueshift of the LSP resonance was observed, respectively. The insights obtained from these experiments were then applied to tune the interparticle separation in nanoparticle pairs, i.e., to tune the resonance wavelength of these plasmonic nanoresonators. Subsequently, single resonators were used to reshape the fluorescence emission spectrum of organic molecules. Besides size and shape, also material parameters such as the surface roughness and the surface material composition influence the optical properties of MNPs. Both aspects are addressed using the example of rough platinum spheres and demonstrating the fabrication of bimetallic core-shell particles. As the material compositon of particles not only influences their optical, but for example also their catalytic or magnetic properties, photochemical metal deposition with in-situ optical LSP read-out builds a bridge to other fields of nanoscience. The presented method is a versatile tool for the fabrication and manipulation of nanostructures, and it is not limited to the field of plasmonics. / Metallische Nanopartikel (MNP) weisen unter Beleuchtung kollektive Schwingungen des Elektronengases auf (sogenannte lokalisierte Oberflächenplasmonen oder LOP). Die dadurch entstehende elektromagnetische Feldverteilung um die Partikel erlaubt die Konzentration von Licht-Materie-Wechselwirkungen auf einen Größenbereich unterhalb des Beugungslimits. In Teil I des vorliegenden Buches werden zwei Anwendungen dieses Konzentrationseffekts beschrieben. Zum einen wird die Verwendung eines einzelnen Partikels als Rastersonde für die optische Nahfeldmikroskopie gezeigt. Zum anderen wird die Fluoreszenzverstärkung in der unmittelbaren Umgebung eines Partikels untersucht. In letzterem Fall liegt der Fokus auf dem Einfluss der Partikelgröße und des Umgebungsmediums auf den Verstärkungsfaktor. Beide Untersuchungen zeigten, dass die Stärke der auftretenden optischen Signale von einer gezielten Steuerung der LOPResonanz profitieren kann. Diese Erkenntnis führte zur Entwicklung einer Methode, welche eine solche spektrale LOP-Steuerung erlaubt. Mit der in Teil II beschriebenen photochemischen Abscheidung von Metall auf einzelne Partikel wurde ein geeigneter Ansatz gefunden. Dabei wird die optisch induzierte Reduktion von Metallsalzkomplexen in einer Lösung ausgenutzt, um dünne Metallschichten auf gezielt ausgewählte Partikel aufzubringen. Der Abscheidungsprozess wird optisch über die Änderung der LOP-Resonanz des belichteten Partikels überwacht. Somit können dessen optische Eigenschaften gezielt in situ eingestellt werden. Mit der beschriebenen Technik können die Größe und die Form einzelner metallischer Partikel beeinflusst werden, was sich in einer Rot- bzw. Blauverschiebung der LOPResonanz äußert. Dieses Prinzip konnte zuerst an sphärischen und ellipsoidalen Goldpartikeln gezeigt werden. Die gewonnen Erkenntnisse wurden dann auf die gezielte Einstellung des Teilchenabstandes in Partikelpaaren übertragen, d. h., die Resonanzwellenlänge solcher plasmonischer Nanoresonatoren wurde gezielt manipuliert. Die Resonatoren konnten in einem zweiten Schritt zur Steuerung des Fluoreszenzspektrums organischer Moleküle eingesetzt werden. Neben Größe und Form spielen auch Materialparameter wie die Oberflächenrauigkeit und das Oberflächenmaterial eine wichtige Rolle für die optischen Eigenschaften der Partikel. Diese Parameter wurden am Beispiel von rauen Platinpartikeln sowie an bimetallischen Kern-Schale-Partikeln untersucht. Da das Oberflächenmaterial nicht nur die optischen, sondern z. B. auch katalytischen und magnetischen Eigenschaften der Partikel beeinflusst, verbindet die vorgestellte Methode die Plasmonik mit vielen anderen Bereichen der Nanotechnologie. Sie stellt eine vielseitige Technik zur Herstellung und Manipulation von Nanostrukturen dar, ohne dabei auf die Nanooptik limitiert zu sein.

No description available.