Dissertations / Theses on the topic 'Synchrotron Radiatio'

This thesis presents interdisciplinary, collaborative research in the field of synchrotron microbeam radiation therapy (MRT). Synchrotron MRT is an experimental radiotherapy technique under consideration for clinical use, following demonstration of efficacy in tumour-bearing rodent models with remarkable sparing of normal tissue. A high flux, X-ray beam from a synchrotron is segmented into micro-planar arrays of narrow beams, typically 25 μm wide and with peak-to-peak separations of 200 μm. The radiobiological effect of MRT and the underlying cellular mechanisms are poorly understood. The ratio between dose in the ‘peaks’of the microbeams to the dose in the ‘valleys’, between the microbeams, has strong biological significance. However, there are difficulties in accurately measuring the dose distribution for MRT. The aim of this thesis is to address elements of both the dosimetric and radiobiological gaps that exist in the field of synchrotron MRT. A method of film dosimetry and microdensitometry was adapted in order to measure the peak-to-valley dose ratios for synchrotron MRT. Two types of radiochromic film were irradiated in a phantom and also flush against a microbeam collimator on beamline BL28B2 at the SPring-8 synchrotron. The HD-810 and EBT varieties of radiochromic film were used to record peak dose and valley dose respectively. In other experiments, a dose build-up effect was investigated and the half value layer of the beam with and without the microbeam collimator was measured to investigate the effect of the collimator on the beam quality. The valley dose obtained for films placed flush against the collimator was approximately 0.25% of the peak dose. Within the water phantom, the valley dose had increased to between 0.7–1.8% of the peak dose, depending on the depth in the phantom. We also demonstrated, experimentally and by Monte Carlo simulation, that the dose is not maximal on the surface and that there is a dose build-up effect. The microbeam collimator did not make an appreciable difference to the beam quality. The measured values of peak-to-valley dose ratio were higher than those predicted by previously published Monte Carlo simulation papers. For the radiobiological studies, planar (560 Gy) or cross-planar (2 x 280 Gy or 2 x 560 Gy) irradiations were delivered to mice inoculated with mammary tumours in their leg, on beamline BL28B2 at the SPring-8 synchrotron. Immunohistochemical staining for DNA double strand breaks, proliferation and apoptosis was performed on irradiated tissue sections. The MRT response was compared to conventional radiotherapy at 11, 22 or 44 Gy. The results of the study provides the first evidence for a differential tissue response at a cellular level between normal and tumour tissues following synchrotron MRT. Within 24 hours of MRT to tumour, obvious cell migration had occurred into and out of irradiated zones. MRT-irradiated tumours showed significantly less proliferative capacity by 24 hours post-irradiation (P = 0.002). Median survival times for EMT-6.5 and 67NR tumour-bearing mice following MRT (2 x 560 Gy) and conventional radiotherapy (22 Gy) increased significantly compared to unirradiated controls (P < 0.0005). However, there was markedly less normal tissue damage from MRT than from conventional radiotherapy. MRT-treated normal skin mounts a more coordinated repair response than tumours. Cell-cell communication of death signals from directly irradiated, migrating cells, may explain why tumours are less resistant to high dose MRT than normal tissue.

Special relativity (SR) determines the properties of synchrotron radiation, but the corresponding mechanisms are frequently misunderstood. Time dilation is often invoked among the causes, whereas its role would violate the principles of SR. Here it is shown that the correct explanation of the synchrotron radiation properties is provided by a combination of the Doppler shift, not dependent on time dilation effects, contrary to a common belief, and of the Lorentz transformation into the particle reference frame of the electromagnetic field of the emission-inducing device, also with no contribution from time dilation. Concluding, the reader is reminded that much, if not all, of our argument has been available since the inception of SR, a research discipline of its own standing.

The purpose of these studies has been to gain a better understanding of the relationships that govern the interfaces of ferromagnetic / ill-V semiconductor heterostructures and other materials. The results here in are expected to promote the development of next generation spin electronic devices which may open the way toward incorporating data processing and storage in a single device through the utilisation of both electron charge and spin. Development ofsuch devices relies a great deal on the quality ofinterface which can be set up between the semiconductor and ferromagnetic structures, as a poor interface leads to difficulty in carrier transport between the materials. Studies into interface magnetism, which can most effectively be carried out using the synchrotron technique of x-ray magnetic circular dichroism (XMCD), have been used to make substantial strides forward in the understanding of the importance of interface quality. It is hoped that these shidies involving synchrotron radiation, predominantly in the area of XMCD, wiJI help the further development ofnew spintronic technologies.

The work described in this thesis is focused on the development of characterization methods for determining the structure of multicomponent metal oxides using synchrotron radiation techniques, in particular, X-ray Absorption Fine Structure (XAFS) and Energy Resolved Electron Yield X-ray Absorption Spectroscopy (EREY– XAS). XAFS is a superior technique for determining the local structure of, for example, transition metals that are used as dopants in very low concentrations. It also provides information on early stages of crystallization processes before a material develops sufficient long range order. Energy resolved XAS was developed as an alternative to conventional transmission and fluorescence techniques which probe mainly the bulk of materials. This techniques yield information about the local structure from the near surface region of materials. The other complementary techniques used for characterization of materials were XRD, Raman spectroscopy, X-ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM). New insights about formation of Bi2MoO6 crystallites from an amorphous gel below 200oC were obtained with a novel in situ setup, in which XAFS and XRD was combined with RAMAN spectroscopy in a single experiment. Combined XRD/XAFS technique was used for determining the growth mechanism of Bi2MoO6 formed under hydrothermal conditions from an amorphous gel. The reaction kinetics was quantified by using the Avrami-Erofe’ev formalism. The surface sensitive of EREY–XAS was performed on several materials in particular chromium doped Fe2O3 catalysts and cobalt substituted aluminophosphates such as CoAlPO-18 and CoAlPO-34. The sensitivity of technique was assessed by comparison with conventional XAS techniques and XPS. Finally, the interactions of a synchrotron X-ray beam with a sample were studied. In particular, the effects of exposure to a monochromatic 10 keV X-ray beam on thermally induced crystallization of lithium disilicate glass were investigated.

Spintronics is an emergent interdisciplinary topic for the studies of spin-based, other than or in addition to charge-only-based physical phenomena, which promises not only new capabilities of electronic devices, but also abundant science. For applied materials, the spin ordering has long been investigated within the context of conventional ferromagnetic materials (FMs), while the study of spin generation, relaxation, and spin-orbit coupling (SOC) in semiconductors (SCs) took off only recently with the advent of spintronics and it is here that many novel materials and FM/SC hybrid structures can find their greatest potential in both science and technology. In the pursuit for such goals, the intrinsic material properties are important indicators and the artificially synthetized hybrid systems (layered FM/SC structures and FM-doped SCs) are valuable models for studying spindependent phenomena and could potentially be used as actual components for an eventual spintronic device. These results are expected to contribute to some of the most fundamental questions of the contemporary spintronic materials research, such as the FM/SC interfacial hybridization and magnetism, the spin and orbital ordering of ferrites, and the fundamental magnetism of doped TIs, and the proximity effects in FM/DMS and FM/doped TI heterostructures.

In the framework of quantum theory the characteristics of synchrotron radiation (SR) are considered. In order to simplify theoretical description the process of radiation is restricted to single-photon emission. For arbitrary quantum transitions the spectral-angular distributions of SR power are given in exact analytical form. Scalar particles (bosons) and particles with spin $\\hbar/2$ (electrons) are treated separately. Special attention is given to the particular transitions, namely, to the transitions to first excited and ground states. It is shown that the components of linear polarization of radiation from electron switch places due to the orientation of spin when the electron jumps to the ground state. This fact can be considered an analytical proof for the presence of $\\pi$-component of quantum radiation in the plane of motion. The radiation emitted from weakly excited particles is thoroughly analysed. To describe the evolution of the profiles of angular distributions various functions are introduced both for two- and three-level systems. For quantum transitions from the first excited state to the ground state the comparative analysis of radiation from bosons and electrons is performed, which helps to estimate the influence of spin and its direction on the characteristics of radiation. The radiation from unpolarized electron is considered separately. Tracking the behavior of effective angles allows to discover the inconsistency of well-known classical conclusion about the concentration of total (summed over spectrum) ultrarelativistic radiation in the plane of motion. It is shown that the effective angles of quantum radiation tend to finite values and do not vanish in ultrarelativistic region. A brief review of classical theory includes an introduction of the new concept, $n$-part of spectrum. In order to find an adequate classical analogue for the radiation from weakly excited particles, the idea to reduce classical spectrum was developed. It turns out that the characteristics of radiation calculated for reduced classical spectrum stay in good quantitative and qualitative agreement with their quantum analogues, at least for single-harmonic and two-harmonic quantum spectra, and classical theory of a reduced spectrum can be claimed representational in this sense. The evolution of maximum in radiation spectrum is considered in separate chapter. A well-known approximation obtained for critical frequency in the framework of classical theory is invalid when quantum corrections enter the picture. But there appears a possibility to find the conditions for the maximum to shift to the highest harmonic of finite quantum spectrum. It is shown that the shifts occur successively starting with primary harmonic in non-relativistic case, and this result remains valid independently of spin. For a scalar particle there exists a fixed set of numbers, which are the critical values of external field, such that the shift of radiation maximum in the spectrum of boson can only happen when the intensity of external field is greater than certain critical value related to corresponding harmonic. If this condition is not satisfied, the position of maximum remains unchanged. It turns out that the presence of spin perturbs this picture, so that the critical values of field intensity depend on the number of initial level.
Consideramos as características da radiação sincrotron (RS) no âmbito da teoria quântica. Para simplificar a descrição teórica do processo de radiação restringimos à consideração da emissão de único fóton. Para transições quânticas arbitrárias, as distribuições espectrais e angulares da potência da RS são dadas de forma analítica exata. Tratamos separadamente partículas escalares (bósons) e com spin ½ (elétrons). Atenção especial é dada às transições particulares, a saber, as transições ao primeiro estado excitado e estado fundamental. É mostrado que os componentes de polarização linear da radiação de elétron se trocam em relação à orientação de spin quando o elétron passa para o estado fundamental. Este fato pode ser considerado como uma comprovação analítica para a presença de -componente da radiação quântica no plano de movimento. Analisamos minuciosamente a radiação emitida pela partícula fracamente excitada. Várias funções são introduzidas para descrever a evolução dos perfis de distribuições angulares para sistemas de dois e três níveis. Para transições quânticas do primeiro estado excitado ao estado fundamental a análise comparativa da radiação de bósons e elétrons é realizada, e isso ajuda à estimar a influência de spin e sua direção sobre as características da RS. A radiação de elétrons não polarizados é considerada separadamente. Observando o comportamento dos ângulos efetivos, é fácil perceber a inconsistência da conclusão clássica bem conhecida sobre a concentração de radiação ultra-relativista total no plano do movimento. Mostramos que os ângulos efetivos da radiação quântica tendem aos valores finitos e não desaparecem na região ultrarelativista. Uma revisão breve da teoria clássica inclui a introdução do conceito novo, isto é a n-parte do espectro. A fim de encontrar um análogo clássico adequado para a radiação das partículas fracamente excitados, a ideia de reduzir o espectro clássico foi desenvolvida. Constatamos que as características da radiação calculadas para o espectro clássico reduzido permanecem em boa concordância, tanto quantitativa quanto qualitativa, com os seus análogos quânticos, pelo menos no que diz respeito aos espectros quânticos de uma ou duas harmônicas. Neste sentido, a teoria clássica do espectro reduzido pode ser chamada de representativa. A evolução do máximo no espectro da radiação é considerada em capítulo separado. A aproximação, comumente considerada na teoria classica para frequência crítica, é inválida quando as correções quânticas entram em cena. Mas existe uma possibilidade de encontrar as condições para o máximo transferir-se à harmônica maior do espectro quântico. É mostrado que as transferências ocorrem sucessivamente, comecando com a harmônica principal no caso não relativístico, e este resultado permanece válido, independentemente de spin. Para uma partícula escalar existe um conjunto fixo dos valores críticos do campo externo, de tal modo que a transferência do máximo da radiação entre duas harmônicas específicas pode acontecer somente quando a intensidade do campo externo é maior do que o valor crítico associado com essas harmônicas. Se essa condição não for satisfeita, a posição do máximo permanece inalterada. Verificamos que a presença de spin perturba esta condição, no caso do elétron os valores críticos da intensidade do campo dependem de número do nível inicial.

The X-ray optics of synchrotron radiation beamlines are considered in this paper. The characteristics of synchrotron radiation which make it the premier source of light for studies in many regions of the electromagnetic spectrum are given. A chapter is devoted to the collimating, focusing and monochromating optics of two X-ray diffraction beamlines at the National Synchrotron Light Source. The beamlines are operated by the Naval Research Laboratory (NRL) and the Oak Ridge National Lab (ORNL). The major optical components of these beamlines are reviewed in regards to their function and their flexibility. A detailed analysis is performed on the NRL X-ray collimating mirror. The mirror is treated as an elastically bent beam. Deflection and slope error equations are developed which relate the shape of the bent mirror to its ideal surface. Visible light diffraction patterns collected from the mirror helped to establish operating conditions which provide good collimation. When the observed patterns are wed to the theoretical calculations, estimates of the average figure error are made. Finally, the effect of a highly collimated synchrotron beam on the reproducibility of the integrated intensities from polycrystalline materials is considered. The calculations show that except for the most fine grained materials, representative intensity measurements can only be made when the sample is permitted to move.
M.S.

This thesis presents experimental data on the fragmentationof gas phase sulfur hexafluoride (SF6) and deutheromethane(CD4) molecules after their interaction with synchrotronradiation in the energy range of 70-200 eV. The data wasobtained using coincidence spectroscopy between energy resolvedelectrons and ions (EREICO).

Degradation of the molecular bond upon selective ionizationof different molecular orbitals has been studied by measuringionic fragments in coincidence with energy selected electrons.Besides the direct ionisation of the orbitals also the indirectprocess, in which the hole is created by the decay of a highlyenergetic core-excited state, was studied. The differencesdetected in the fragmentation after the direct and indirectionisation of a selected orbital can be related, in some cases,with the relaxation of the nuclei in the potential energysurface of the core excited state during its lifetime, thusproviding information on the neutral core excited state.

An experimental set-up capable of photon inducedfluorescence spectroscopy (PIFs) studies of core excitedmolecules in the visible range has been constructed. Thistechnique can yield complementary information to the EREICOdata about the energy distribution in the fragmentation sincethe internal energy of excited emitted fragments that decay inthe visible can be measured. It also allows the detection ofpossible neutral fragments.

This thesis contains two parts. The first part concerns the research work on free molecules using synchrotron-radiation-related techniques. Auger electron spectra of two free open-shell molecules, O₂ and NO, were studied experimentally and theoretically. Photoionization experimental technique with tunable synchrotron radiation source was used to induce core-level electron ionization and obtain the KVV normal Auger electron spectra. A quantitative assignment of O₂ normal Auger spectrum was obtained by applying ab initio CI calculations and LVI Auger line shape simulations including the bond length dependence of Auger transition rates. The photon energy dependence of normal Auger electron spectra was focused on with photon energies in the vicinities of core-ionization threshold energies. Consequently, the MAPCI (Molecular Auger Post Collision Interaction) theory was developed. Taking the near-threshold O₂ normal Auger spectrum as an example, the two extreme cases of MAPCI effect, “atomic-like PCI” and “molecular PCI”, were discovered and discussed. The effect of shape resonance on near-threshold molecular normal Auger spectrum was discussed taking NO near threshold normal Auger spectra as example.

The second part deals with research work on the chemisorption of small epoxy organic molecules, ethylene oxide, methyl oxirane, on Si (100) surfaces. Synchrotron radiation related techniques, UPS, XPS and NEXAFS, were applied. Based on the valence photoemission spectra, C 1s and Si 2p XPS spectra, the epoxy ring opening reactions of these molecules in chemisorption process were proved. Further tentative search for the surface-adsorbate CDAD effect was performed, and no evident circular dichroism was confirmed.

Directional Compton profile measurements of aluminium and chromium have been performed with 60 keV and 412 keV γ-radiation to assess the complementarity of the 241Am and 198Au spectrometer systems in common use by experimentalists. Revision of the data reduction procedure has yielded symmetrical Compton profiles within experimental error for the first time. The effects of exchange and correlation on theoretical Compton profiles calculated within the local density approximation have been evaluated via the Lam-Platzman correction and applied to existing transition metal results. Novel experiments using circularly polarised synchrotron radiation to detect the magnetic Compton profiles of iron and nickel have been performed successfully.

Le rayonnement synchrotron est l'un des facteurs clés du grand succès de la cristallographie macromoléculaire au cours des dernières décennies. Plus de 90% de toutes les structures de protéines de la base de données PDB a été résolu par cristallographie en utilisant des sources de rayonnement synchrotron et environ 95% d'entre elles a été déterminé à partir de cristaux congelés.Cependant, les structures déterminées par des techniques de congélation sont limitées par la nature statique des cristaux congelés. Avec le développement récent des sources de RX produites par lasers à électrons libres (XFEL), qui sont en mesure de produire des impulsions femtosecondes très intenses de rayons X, l'ère de la « diffraction avant destruction » et de la cristallographie sérielle femtoseconde utilisant des micro- ou nano- cristaux a commencé (SFX).Au cours du procédé SFX un cristal de protéine n'est exposé qu'une fois au faisceau de rayons X pendant quelques dizaines de femtosecondes avant qu'il ne soit complètement détruit. Les données sont collectées à partir de cristaux orientés de façon aléatoire par rapport au faisceau de rayons X; une seule exposition par cristal est possible. Afin de recevoir un ensemble de données plus complet, de nouvelles techniques d'analyse de données de diffraction ont été développées.La première expérimentation réussie du procédé (SFX) a été réalisée au LCLS à Stanford en décembre 2009 sur des cristaux du photosystème I et de lysozyme. Les experts en cristallographie des installations XFEL peuvent déterminer des structures de protéines à température ambiante presque exemptes de dégâts d'irradiation, en raison des pulses de FEL femtosecondes si brèves, qu'ils passent à travers l'échantillon avant que des dommages de rayonnement importants ne se produisent.Après la présentation des premières expériences SFX réussies, des efforts pour effectuer une cristallographie en série de cristaux de taille de l’ordre des micromètres à température ambiante ont commencé au sein des synchrotrons. Une première tentative de cristallographie synchrotron en série et à température ambiante a été tentée à PETRA III à DESY à Hambourg. Cette méthode a été nommée SMX (synchrotron serial millisecond crystallography), où des milliers d'échantillons sont collectés à partir de cristaux individuels passant par le faisceau à rayons X. Avec le développement des techniques de cristallographie série à température ambiante au sein des synchrotrons, la répartition de la dose sur un grand nombre de cristaux compense l’augmentation des dommages liés à l’irradiation à température ambiante.Bien que les sources de rayonnement synchrotron n'atteindront probablement jamais la même luminosité que les impulsions de rayons X comme dans les XFELs, elles ont un certains nombre d'avantages. L'un d'eux est la flexibilité de configuration grâce au paramétrage de lignes de faisceaux microfocus. Un autre est que plusieurs expositions par cristal sont possibles. En outre, les synchrotrons sont plus répandus dans le monde: la probabilité d'obtenir un temps d'expérimentation dans un synchrotron est plus élevée que pour une installation XFEL. En effet, maintenant deux installations XFEL sont ouvertes pour les utilisateurs .L'objectif de cette thèse est de proposer et de mettre en œuvre des méthodes qui permettront de recueillir des données en utilisant l'approche de la cristallographie série à l'installation synchrotron européen (ESRF, Grenoble, France). Cette thèse présente différentes techniques pour réaliser la cristallographie sérielle sur la ligne ID13 à l’ESRF. L'objectif était de développer la cristallographie sérielle sur synchrotron basée sur la numérisation micro-diffraction pour démontrer que les sources de rayonnement synchrotron peuvent être utilisées comme un instrument de routine pour cette technique avec des protéines globulaires et membranaires. Les aspects de la collecte de données et leur traitement seront également discutés
Synchrotron radiation is one of the key factors for the tremendous success of macromolecular crystallography during the past decades. More than 90 % of all protein structures in PDB database were solved by crystallography using synchrotron radiation sources and around 95 % of them were determined from cryocooled crystals1,2. A whole data set can be collected from one flash-cooled crystal. Data-collection at cryogenic temperatures drastically reduces radiation damage effects. However, structures determined using cryo freezing techniques are limited by static nature of frozen crystals.With the recent development of X-ray free-electron laser facilities (XFELs), which are able to produce extremely intense femtosecond X-ray pulses, the era of “Diffraction before destruction” and serial femtosecond crystallography (SFX) for micro-/nano-sized crystals has begun3. In the SFX technique a protein crystal is only exposed once to the X-ray beam for tens of femtoseconds before it is completely destroyed. The data is collected from randomly oriented crystals that are exposed to the X-ray beam; only one shot per crystal is possible. In order to receive a complete data set, new data analysis techniques that are capable of dealing with large quantities of diffraction data have been developed. First experiment where serial femtosecond crystallography (SFX) approach was first carried out was performed at the Linac Coherent Light Source (LCLS, Stanford, USA) in December 2009 on photosystem I and lysozyme crystals4,5,6. At XFELs facilities crystallographers can perform room temperature structure determination of proteins almost free of radiation damage, due to the fact that femtosecond flashes of FEL is so brief, that it passes through the sample before the significant radiation damage occurs.After presenting first successful experiments with SFX technique, efforts to perform serial crystallography of micron-sized crystals at room-temperature started at synchrotron sources. First attempt to perform synchrotron room-temperature serial crystallography has been done at PETRA III at DESY in Hamburg using glass capillary based microfluidics7. This method was named synchrotron serial millisecond crystallography (SMX), where thousands of patterns are collected from individual crystals passing through the X-ray beam8. With development of room-temperature serial crystallography techniques at the synchrotrons, the exposure distributed on a large number of crystals in the sample, which helps compensating the effect of increased radiation damage at ambient temperature.Although synchrotron sources most certainly will never reach the same brightness of X-ray pulses like XFELs, they have some advantages. One of them is possibility to perform any set up due to the flexibility of the parameters of microfocus beamlines. Another advantage of SMX is that several shots per crystals are possible. Also should be mentioned that synchrotrons are more widespread all over the world, so possibility to get a beamtime at the synchrotron is much higher than at XFELs, because currently only two XFEL facilities are open for users (LCLS, USA and SACLA, Japan).The aim of this dissertation is to propose and to implement methods that will allow to collect data using the serial crystallography approach at the European synchrotron radiation facility (ESRF, Grenoble, France). This dissertation presents different techniques to perform synchrotron serial crystallography at ID13 beamline. The goal was to develop synchrotron serial crystallography based on scanning micro-diffraction to demonstrate that synchrotron sources can be used as a routine instrument to perform serial crystallography with soluble and membrane proteins. The aspects of the data collection and data processing also will be discussed

In this manuscript we describe a novel method to map the two-dimensional transverse coherence of an x-ray beam using the dynamical near-field speckles formed by scattering from colloidal particles. The method is suitable for live beam diagnostics, allowing time-resolved measurements.

This Licentiate thesis presents research accomplished at theSection of Atomic and Molecular Physics at the Royal Instituteof Technology in Stockholm using photon induced fluorescencespectroscopy (PIFS) during the last two years.

The main results presented are summarized:

- Neutral photodissociation in CO was observed aftersynchrotron photon excitation in the range 19-26 eV bycollecting dispersed fluorescence from excited neutral C atoms.Follow-up ab initio calculations point out CO Rydberg seriesconverging to the CO+ C and D states as precursors.

- The branching ratio between N2 + (B-X)(v’=1,v’’=2) and (v’=0,v’’=1)transitions in the 20-46 eV energy range reveals strongnon-Franck-Condon effects. Ab initio calculations indicate thatthe autoionization of certain superexcited states areresponsible for some of the structures present in the branchingratio curve, confirming the important role of non-Rydbergdoubly excited resonant states (NRDERS) in de-excitationprocesses above the ionization potential.

- Photon induced neutral dissociation processes in NO arereported. Neither Rydberg series nor other molecular states inNO known so far can account for the collected data. From abinitio calculations more information regarding the NO precursorstates and the mechanism behind the observed neutraldissociation were obtained.

- The details of a new experimental set-up for gas phasefluorescence measurements using synchrotron radiation aredescribed. It is able to perform simultaneous measurements ofdispersed and total fluorescence in the visible range. Thefirst results obtained with this set-up are presented,concerning fluorescence after excitation of the N2 molecules inthe N 1s edge.

These four studies conform the set of papers enclosed in theLicentiate thesis.

Finally a pre-study to further apply PIFS to speciespreviously excited by microwave discharge is included as futureplans.

This thesis presents experimental studies of gas phasemolecular relaxation after excitation with synchrotron photonsin the 15-35 eV and in the 70-350 eV regions.

In the 15-35 eV region, molecular relaxation by neutraldissociation processes and non

Franck-Condon effects in N2 and O2 molecules have beenstudied by means of dispersed fluorescence and photoelectronspectroscopy experimental techniques, respectively. From thedispersed fluorescence data, excitation functions for themeasured atomic fluorescence spectra have been obtained. Fromthe recorded photoelectron spectra vibrational branching ratioshave been produced. The results obtained reveal that Rydbergseries and singly and doubly excited valence states of theappropriate symmetry energetically accessible in the studiedregion and interactions between themaccount for most of theobserved effects in these two type of experiments.

In the 70-350 eV range, molecular relaxation processesresulting in fragmentation of CD4 and SF6 after absorption ofsynchrotron light have been studied by energy resolved electronion coincidence technique using a multicoincidence experimentalstation developed by our group during the last five years forsuch type of experiments. The coincidence measurements yieldedmass spectra from which information about the kinematics of thedetected fragments has been deduced by means of Monte Carlosimulations of the experimental peak shapes. The obtainedresults show completely different dissociation patternsdepending on the molecular electronic states studied. Thesepatterns reflect the bonding properties of the excited orbitalsand they permit the description and in some cases theidentification of the different molecular relaxation pathwaysobserved. The achievements presented in this thesis exemplifythe potential of the multicoincidence station used in thereported experiments.

This thesis summarises the experimental results on molecular spectroscopy of gas phase molecules using synchrotron radiation in the UV- VUV and soft-X rays regions. The results of applying Photon Induced Fluorescence Spectroscopy (PIFS) to D2, H2S, H2O and pyrimidine are presented and discussed. Both inner and outer shell excitations of free molecules lead to different relaxation processes. However, a common result is that when the molecule breaks and the resulting neutral fragments are left in an excited state, they might fluoresce in the UV- Vis range. PIFS technique has two main advantages, it permits to detect neutral fragments and to identify the fluorescing species. From this fact, we can infer dissociation channels and trace back the electronic processes that led to the fluorescence. For these molecules we have analysed and interpreted both dispersed and undispersed fluorescence. What motivates our work is the lack of fluorescence studies and in a more general sense, to contribute to the knowledge of important molecules for life such as water and pyrimidine.

A new experimental set-up for gas phase fluorescence studies using synchrotron radiation has been designed and constructed to perform simultaneously total and dispersed fluorescence measurements.

Neutral photodissociation of CO has been investigated after excitation with 19-26 eV photons. Fluorescence from 3p 3P, 3p 3S and 3p 1D excited states in carbon was recorded and interpreted by ab initio calculations. The population and dissociation of states belonging to the C and D Rydberg series in CO seem to explain the production of the observed triplet states but not the 3p 1D state.

Neutral photodissociation of NO is reported in the 17-26 eV energy range. No known molecular states can account for the collected data. New information regarding the precursor states of the observed neutral dissociation is provided by ab initio calculations.

Autoionization of superexcited states in molecular nitrogen is evidenced by strong deviations of the Franck-Condon ratio in the fluorescence of the N2+ B state. Ab initio calculations predict the existence of autoionizing-excited states that may account for some of the observed structures in the 20-46 eV energy range.

Selective molecular fluorescence from the npó1Óu+ and npð 1Ðu (n=3-7) Rydberg levels to the E,F 1Óg+ state in H2 was recorded and rotationally analyzed. Vibrational levels of the E,F 1Óg+ state (vEF =0,1,3,6-10) are determined. The predissociation of npð 1Ð+ levels is observed in agreement with the literature.

Fragmentation of SF6 was investigated after excitation with 25–80 eV photons. Dispersed fluorescence measurements reveal the emission of S, S+, F and F+ excited atoms. These fragments are produced after single, double and triple excitations as well as direct ionizations and shake-ups in SF6.

Photoabsorption and fluorescence yield have been measured in SF5CF3 using 10-30eV photons. The photoabsorption spectrum can be explained in terms of its similarities to those of the SF6 and CF4 molecules. The dispersed and un-dispersed fluorescence resemble those of the CF3X family. Several features suggest the migration of an F atom across the S-C bond that fragments the molecule producing excited CF4.

Doubly excited states of H2 have been investigated in the range of 26-60 eV by monitoring Balmer á emission. The experimental data show the already known emission correlated with the fragmentation of the Q1 and Q2 states, and new features which could be attributed to dissociative photoionization and higher lying doubly excited states Qn (n>2) of the hydrogen molecule

La spintronique multifonctionnelle est une nouvelle direction d'avancement pour aller au-delà des limites de l'électronique moderne. Il vise à développer des dispositifs qui seraient sensibles à plus d’un stimulus et/ou ont un signal multi-réponse. Dans cette thèse, nous explorons cette voie multifonctionnelle émergente en combinant l’électronique de spin et les systèmes organiques pour ouvrir la voie vers des dispositifs polyvalents. Nous étudions la formation d'une spinterface dans le système Co/manganèse-phthalocyanine. Nous proposons l'introduction de multifonctionnalités intrinsèques en utilisant des matériaux à transition de spin. Nous développons une nouvelle approche de fonctionnalisation pour ajuster leurs propriétés vers des applications. Nous proposons un contrôle fonctionnel externe sur une spinterface en utilisant un substrat multiferroïque. Dans le cadre de cette thèse, un insert polyvalent à température variable a été développé à la ligne de lumière DEIMOS du synchrotron SOLEIL. Nous démontrons comment il peut être utilisé pour sonder des atomes actifs dans n'importe quel dispositif électronique
Multifunctional spintronics is a new direction of advancement beyond the limits of modern electronics. By combining elementary charge of an electron and its spin, it aims to develop devices which would be sensitive to more than one stimuli and/or have multiresponse signal. In this thesis, we explore the multifunctional potential emerging while combining spin electronic and organic systems to pave the way towards multipurpose devices. First, we study formation of a ferromagnetic/organic spinterface in Co/manganese-phthalocyanine system. We propose introduction of intrinsic multifunctionality by using spin crossover materials. We develop a novel functionalization approach for tuning their properties towards device applications. We propose an external functional control over any hybrid spinterface by using multiferroic substrate. In the framework of this thesis, a Versatile Variable Temperature Insert was developed at the DEIMOS beamline of the SOLEIL synchrotron. We demonstrate how it can be used to probe active atoms in any microelectronic device

This thesis describes an investigation into the performance of different schemes for generating short x-rays pulses via synchrotron radiation emission. A review is given of the methods that have been previously proposed for this task. From this review, three leading schemes are selected for in-depth investigations, each of which explores the boundary of what is presently achievable in accelerator-based light sources. The first scheme generates short x-ray pulses by operating an electron storage ring in a quasi-isochronous state using a ‘low-alpha’ lattice. High and low emittance lattices are developed, studied through simulation and then implemented on the Diamond storage ring. Beam dynamics and bunch length measurements are presented for a variety of machine conditions, and an assessment is made of the minimum practically achievable bunch length for stable user operation. Radiation pulses of 1 ps r.m.s. are demonstrated using this scheme. The second and third schemes investigate performance limits for a linac-based light source through numerical simulations. The first of these generates ultra-short pulses by passing a highly compressed electron bunch through a long undulator to radiate in the ‘single-spike’ regime. A comparison is made with theoretical predictions for the required electron bunch length to operate in this way, which highlights the need for accurate start-to-end simulations. The final scheme generates ultra-short x-ray pulses through laser manipulation of the electron bunches. The modulated electrons pass through a long undulator with tapered gap, such that only the centre of the modulated portion experiences high free-electron laser (FEL) gain. A method to enhance the FEL output from this scheme using a wavelength filter and grating-compressor is investigated. The sensitivity of the two schemes to jitter sources is determined, and it is demonstrated both schemes are capable of generating GW-level, fully coherent sub-fs soft x-ray pulses. Such pulses would open up the development of time-resolved science to new regimes.

The growth mode and the electronic and magnetic properties of nanoscale Mn structures, in the form of islanded films and deposited mesoscopic clusters, have been investigated using synchrotron radiation. The Volmer-Weber growth of Mn films was studied by modelling the surface reflectivity in the extreme ultraviolet region (6-36 nm). The island growth at 423 K showed a change in growth mode as a function of coverage. Spin Polarised Photoelectron Diffraction (SPPED) from thick Mn revealed that the short range magnetic order (SRMO) is lost at a temperature of 505 K, 5.3 times the bulk Neel Temperature. Results for an islanded film, where the average island size was 6 nm, showed surprisingly that SRMO breaks down at the bulk Mn Neel temperature, with the interpretation that a complete loss of magnetic order is induced down to atomic length scales in the mesoscopic system. Core level and valence band photoemission from islanded Mn films have shown modified lineshapes in comparison to the bulk. The peak asymmetry of the 3p core level increases with decreasing particle size indicating a perturbation of the collective electron response upon the production of a core hole. The valence band and 3p core level photoemission also showed marked changes in lineshape as the temperature was increased through the bulk Mn Neel temperature. Mesoscopic Mn clusters have been deposited in-situ with the use of a high temperature gas aggregation source. Both unfiltered and size-selected 2.5 nm clusters have been investigated. Photoemission from exposed clusters showed significant changes in the Mn 3s core level line shape with respect to the bulk, interpreted as an enhanced atomic magnetic moment. Unfiltered Mn clusters were also embedded in a V matrix revealing a satellite structure in the 3s photoemission from V suggesting that the Mn clusters magnetically polarise surrounding V atoms.

In this thesis two single molecule magnets based on the dodecamanganese (III, IV) cluster, with either benzoate or terphenyl-4-carboxylate ligands have been studied on the Au(111) and rutile TiO2(110) surfaces. We have used in situ electrospray deposition to produce a series of surface coverages from a fraction of a monolayer to multilayer films in both cases. X-ray absorption spectroscopy measured at the Mn L-edge (Mn 2p) has been used to study the effect of adsorption on the oxidation states of the manganese atoms in the core. In the case of the enzoate-functionalized complex, reduction of the manganese metal centres is observed due to the interaction of the manganese core with the underlying surface. In the case of terphenyl-4 carboxylate, the presence of this much larger ligand prevents the magnetic core from interacting with either the gold or the titanium dioxide surfaces and the characteristic Mn3+ and Mn4+ oxidation states necessary for magnetic behaviour are preserved. In contrast to the single molecule magnets where no charge transfer between the molecules and the substrates or within the molecules themselves were wanted, the molecules of bi isonicotinic acid and the giant zinc porphyrin nanorings have been studied on rutile TiO2(110) and Au(111) surfaces in the pursuit of charge transfer. In the case of the bi-isonicotinic acid it is studied on the rutile TiO2(110) where the technique of resonant inelastic X-ray scattering was been employed. Here we introduce the core-hole clock implementation to estimate the charge transfer from the molecule to the substrate. We verify previous results of ultrafast charge transfer in the sub-femtosecond regime (2.9 ± 0.3 femtoseconds) out of the LUMO+1 orbital. When the higher lying state of the LUMO+2 state is probed charge transfer out of this state and to the substrate is possibly there, but it is not possible to resolve it since it is masked by other effects originating from the inelastic scattering of the system. Furthermore, we see potential charge transfer within the molecule itself and new states observed in the inelastic scattering. Finally, zinc porphyrin nanorings were investigated on two surfaces of rutile TiO2(110) and Au(111). The techniques used here were X-ray photoemission spectroscopy and resonant photoemission spectroscopy. When the rutile TiO2(110) surface was employed hardly any participator decay was present suggesting charge transfer within the molecule itself or to the surface. This is further backed up by the fact that all of the core-excited unoccupied states are found to overlap energetically with the unoccupied states of the substrate, facilitating charge transfer out all the core-excited states. In the case of the Au(111) surface somewhat similar results are found, having all the core-excited states of the molecule located within the unoccupied states of the substrate, which again will facilitate charge transfer out all the core-excited states of the molecule. When the Au(111) substrate was employed the technique of near edge X-ray absorption fine structure was used to investigate the geometric orientation of the molecule on the surface. With the result of 86◦ ± 10◦ to the surface normal we verify previous scanning tunneling microscopy measurement that the zinc porphyrin nanorings will take a at lying orientation on the gold substrate.

Heterogeneous catalysis is a large and important field of research, and is especially of interest to the project sponsors Johnson Matthey (JM). This EngD project focused on studying catalytic materials of interest to JM in order to investigate the metal support interaction and determine the effects of various reaction conditions. The key techniques used in this work are synchrotron radiation based, such as X-ray absorption spectroscopy (XAS), X-ray diffraction (XRD) as well as combinations of techniques. A variety of catalytic materials have been investigated using synchrotron X-ray techniques and conventional laboratory analytical techniques. Understanding these processes will allow for the tailoring of catalyst design and modification of support materials that will lead to improved and more efficient catalytic materials in the future. Supported platinum group metals were studied during reduction using in situ XAS. The materials were prepared through sequential deposition on an alumina support of first the platinum group metal then a ceria layer; this additional layer of ceria was deposited to cover the metal particles, limiting movement and gas transfer processes. The effect of the MSI on the reduction of Pd nanoparticles supported on a variety of inorganic materials in order to determine the structure of metal particles was also explored using in situ XAS. A combination of the LIII- and K-edge analysis was utilised to provide a better understanding of metal support interaction and the changes in the electronic structure for supported Pd nanoparticles. Other materials investigated include zinc oxide nanoparticles, which are important for a variety of applications due to their semi-conductor properties. Additionally AuCu bimetallic clusters were investigated in situ during reduction, calcination and during the catalytic oxidation of propene. The use of XAS allowed for the probing of the extent of the metal alloying and the effect on the propene catalysis.

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.

2011/2012
Digital imaging systems for medical applications must be based upon highly efficient detectors to ensure low patient dose. This is considerably important, especially in mammography, because the high sensitivity of the breast to radiation. A mammoraphy system must also provide high spatial and contrast resolution to be able to detect important structures related to breast malignancies. The work performed and described in this thesis is the development of a readout system for a detector optimised for clinical mammography with synchrotron radiation. The detector called PICASSO (Phase Imaging for Clinical Application with Silicon detector and Synchrotron radiatiOn) is developed mainly for the mammography station of the SYRMEP beamline. The detector described in this work is based on Silicon microstrip sensors that are illuminated edge-on. The incoming beam impinging the detector is parallel to the strips of its sensors. This configuration permits high detection efficiency in the energy range that is of interest for mammography. Moreover, the Silicon sensors also allow direct conversion of X-rays. The readout electronics of the Picasso detector works on single-photon counting mode. That is, only signals from photons that are equal or greater than a pre-set threshold are counted, and low freqency noise are automatically rejected. The visibility of small details, normally valuable in mammograms, are maximised because the system is quantum limited, ie, the quality of the image is limited only by the intrinsic fluctuation of the detected photons. Picasso has four layers, each containing three detector modules. The layers are grouped into pairs and arranged one in front of the other along the beam of propagation. The pairs are controlled separately but are working in parallel. The system is a modular detector that implements a read-out system with MYTHEN II ASICs, an embedded Linux-based controller board and a Scientific Linux acquisition workstation. The developed system architecture and its characteristics will be presented. Preliminary imaging tests were perfomed and results with the new system will be presented. Standard mammographic phantoms were imaged and good quality images were obtained at doses comparable with what is delivered in conventional full field mammographic systems. The whole system was able to sustain fast acquisition speeds up to 10ms/frame and runs stable until a breast-equivalent length acquisition is accomplished. A delay between frame of 150μs and delay between controllers of around 750μs is achieved. Phase-contrast imaging has revolutionized the face of mammography with synchrotron radiation in the last ten years as the first clinical phase has been successfully implemented in our facility. This initial step made use of commercial screen-film system producung promising results. Thanks to the coherence and monochromaticity of light coming from synchrotron sources that edge-enhancement in the image is achieved due to phase effects. The compatibility of the Picasso detector to phase-contrast imaging with other novel techniques has also been evaluated in line with this project. Phase-contrast was well demonstrated with the system, details of which will be fully described.
XXV Ciclo
1980

Abstract The present thesis investigates the electronic structure of selected atoms and molecules in vapor phase. Electron spectroscopy is applied for studying the electronic transitions following excitation and ionization with electron and photon bombardment. The work focuses on the photoionization and Auger decay of selected noble gasses, and on the photoionization and Auger decay of core ionized or resonant excited alkali halide molecules. The experimental results are compared with theoretical predictions.