<p>In this thesis we have performed core-electron spectroscopy studies of gas phase molecular systems starting with smaller diatomic, continuing with triatomic and extending our research to more complex polyatomic ones. We can subdivide the results presented here into two categories: the first one focusing on electronic fine structure and effect of the chemical bonds on molecular core-levels and the other one dealing with nuclear dynamics induced by creation of a core hole. In our research we have mostly used synchrotron radiation based techniques such as X-ray Photoelectron (XPS), X-ray Absorption (XAS), normal and Resonant Auger (AES and RAS, respectively) and Energy-Selected Auger Electron PhotoIon COincidence (ES-AEPICO) spectroscopies.</p><p>We have demonstrated that resonant Auger spectroscopy can be used to aid interpretation of the features observed in XAS for Rydberg structures in the case of Cl₂ and C1s⁻¹π*¹ states of allene molecules. The combined use of high-resolution spectroscopy with <i>ab initio</i> calculations can help the interpretation of strongly overlapped spectral features and disentangle their complex profiles. This approach enabled us to determine the differences in the lifetimes for core-hole 2p sublevels of Cl₂ which are caused by the presence of the chemical bond. We have shown that contribution in terms of the Mulliken population of valence molecular orbitals is a determining factor for resonant enhancement of different final states and fragmentation patterns reached after resonant Auger decays in N₂O.</p><p>We have also performed a systematic study of the dependence of the C1s resonant Auger kinetic energies on the presence of different substituents in CH₃X compounds. For the first time we have studied possible isomerization reaction induced by core excitation of acetylacetone. We could observe a new spectral feature in the resonant Auger decay spectra which we interpreted as a signature of core-excitation-induced keto-enol tautomerism.</p>

<p>Clusters are finite ensembles of atoms or molecules with sizes in the nanometer regime (<i>i.e.</i> nanoparticles). This thesis present results on the geometric and electronic structure of homogeneous and heterogeneous combinations of atoms and molecules. The systems have been studied with synchrotron radiation and valence, core and Auger electron spectroscopic techniques.</p><p>The first theme of the thesis is that of mixed clusters. It is shown that by varying the cluster production technique both structures that are close to that predicted by equilibrium considerations can be attained as well as far from equilibrium structures.</p><p>Electronic processes following ionization constitute the second theme. The post-collision interaction phenomenon, energy exchange between the photo- and the Auger electrons, is shown to be different in clusters of argon, krypton and xenon. A model is proposed that takes polarization screening in the final state into account. This result is of general character and should be applicable to the analysis of core level photoelectron and Auger electron spectra of insulating and semi-conducting bulk materials as well.</p><p>Interatomic Coloumbic Decay is a process that can occur in the condensed phases of weakly bonded systems. Results on the time-scale of the process in Ne clusters and mixed Ar/Ne clusters are herein discussed, as well observations of resonant contributions to the process. In analogy to Auger <i>vis-à-vis</i> Resonant Auger it is found that to the ICD process there is a corresponding Resonant ICD process possible. This has later been observed in other systems and by theoretical calculations as well in subsequent works by other groups.</p><p>Delocalization of dicationic valence final states in the hydrogen bonded ammonia clusters and aqueous ammonia has also been investigated by Auger electron spectroscopy. With those results it was possible to assign a previously observed feature in the Auger electron spectrum of solid ammonia.</p>

Clusters are finite ensembles of atoms or molecules with sizes in the nanometer regime (i.e. nanoparticles). This thesis present results on the geometric and electronic structure of homogeneous and heterogeneous combinations of atoms and molecules. The systems have been studied with synchrotron radiation and valence, core and Auger electron spectroscopic techniques. The first theme of the thesis is that of mixed clusters. It is shown that by varying the cluster production technique both structures that are close to that predicted by equilibrium considerations can be attained as well as far from equilibrium structures. Electronic processes following ionization constitute the second theme. The post-collision interaction phenomenon, energy exchange between the photo- and the Auger electrons, is shown to be different in clusters of argon, krypton and xenon. A model is proposed that takes polarization screening in the final state into account. This result is of general character and should be applicable to the analysis of core level photoelectron and Auger electron spectra of insulating and semi-conducting bulk materials as well. Interatomic Coloumbic Decay is a process that can occur in the condensed phases of weakly bonded systems. Results on the time-scale of the process in Ne clusters and mixed Ar/Ne clusters are herein discussed, as well observations of resonant contributions to the process. In analogy to Auger vis-à-vis Resonant Auger it is found that to the ICD process there is a corresponding Resonant ICD process possible. This has later been observed in other systems and by theoretical calculations as well in subsequent works by other groups. Delocalization of dicationic valence final states in the hydrogen bonded ammonia clusters and aqueous ammonia has also been investigated by Auger electron spectroscopy. With those results it was possible to assign a previously observed feature in the Auger electron spectrum of solid ammonia.

In this thesis we have performed core-electron spectroscopy studies of gas phase molecular systems starting with smaller diatomic, continuing with triatomic and extending our research to more complex polyatomic ones. We can subdivide the results presented here into two categories: the first one focusing on electronic fine structure and effect of the chemical bonds on molecular core-levels and the other one dealing with nuclear dynamics induced by creation of a core hole. In our research we have mostly used synchrotron radiation based techniques such as X-ray Photoelectron (XPS), X-ray Absorption (XAS), normal and Resonant Auger (AES and RAS, respectively) and Energy-Selected Auger Electron PhotoIon COincidence (ES-AEPICO) spectroscopies. We have demonstrated that resonant Auger spectroscopy can be used to aid interpretation of the features observed in XAS for Rydberg structures in the case of Cl2 and C1s−1π*1 states of allene molecules. The combined use of high-resolution spectroscopy with ab initio calculations can help the interpretation of strongly overlapped spectral features and disentangle their complex profiles. This approach enabled us to determine the differences in the lifetimes for core-hole 2p sublevels of Cl2 which are caused by the presence of the chemical bond. We have shown that contribution in terms of the Mulliken population of valence molecular orbitals is a determining factor for resonant enhancement of different final states and fragmentation patterns reached after resonant Auger decays in N2O. We have also performed a systematic study of the dependence of the C1s resonant Auger kinetic energies on the presence of different substituents in CH3X compounds. For the first time we have studied possible isomerization reaction induced by core excitation of acetylacetone. We could observe a new spectral feature in the resonant Auger decay spectra which we interpreted as a signature of core-excitation-induced keto-enol tautomerism.

Ever since the discovery of exotic phenomena like high temperature (Tc) superconductivity in the cuprates and colossal magnetoresistance in the manganites, strongly correlated electron systems have become the center of attention in the field of condensed matter physics research. This renewed interest has been further kindled by the rapid development of sophisticated experimental techniques and tremendous computational power. Computation plays a pivotal role in the theoretical investigation of these systems, because one cannot explain their complicated phase diagrams by simple, exactly solvable models. Among the plethora of experimental techniques, various kinds of high energy electron spectroscopies are fast gaining importance due to the multitude of physical properties and phenomena which they can access. However the physical processes involved and the interpretation of the spectra obtained from these spectroscopies are extremely complex and require extensive theoretical modelling. This thesis is concerned with the theoretical modelling of a certain class of high energy electron spectroscopies, viz. the core-level electron spectroscopies, for strongly correlated systems of various kinds. The spectroscopies covered are Auger electron spectroscopy (AES), core-level photoemission spectroscopy (core-level PES) and X-ray absorption spec- troscopy (XAS), which provide non-magnetic information, and also X-ray magnetic circular and linear dichroism (XMCD and XMLD), which provide magnetic information. .

Aqueous solutions were studied using photoelectron and Auger spectroscopy, based on synchrotron radiation and a liquid micro-jet setup. By varying the photon energy in photoelectron spectra, we depth profiled an aqueous tetrabutylammonium iodide (TBAI) solution. Assuming uniform angular emission from the core levels, we found that the TBA+ ions were oriented at the surface with the hydrophobic butyl arms sticking into the liquid. We investigated the association between ions and their neighbors in aqueous solutions by studying the electronic decay after core ionization. The (2p)−1 decay of solvated K+ and Ca2+ ions was studied. The main features in the investigated decay spectra corresponded to two-hole final states localized on the ions. The spectra also showed additional features, related to delocalized two-hole final states with vacancies on a cation and a neighboring water molecule. These two processes compete, and by comparing relative intensities and using the known rate for the localized decay, we determined the time-scale for the delocalized process for the two ions. We compared to delocalized electronic decay processes in Na+, Mg2+, and Al3+, and found that they were slower in K+ and Ca2+, due to different internal decay mechanisms of the ions, as well as external differences in the ion-solute distances and interactions. In the O 1s Auger spectra of aqueous metal halide solutions, we observed features related to delocalized two-hole final states with vacancies on a water molecule and a neighboring solvated anion. The relative intensity of these feature indicated that the strength of the interaction between the halide ions and water correlated with ionic size. The delocalized decay was also used to investigate contact ion pair formation in high concentrated potassium halide solutions, but no concrete evidence of contact ion pairs was observed. / Felaktigt tryckt som Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 726

This thesis describes two different sample preparation strategies for inductively coupled plasma atomic emission spectrometry (ICP-AES), and their ability regarding multi element quantification in complex samples. Sensitivity, repeatability, reproducibility and accuracy were investigated. The aim was to increase the over all efficiency, the speed of analysis, and/or the sensitivity of the analytical method. The intention was to measure analytes with concentrations ranging from ng/g to mg/g simultaneously. The aim was additionally to study chemical and physical processes occurring during the sample preparation, the sample transport to the plasma, and the atomization therein. In the first sample preparation strategy, a hydrophilic highly cross-linked iminodiacetate-agarose adsorbent, IDA-Novarose, was used for preconcentration of metal ions, and matrix elimination in natural water samples. The sorbent was synthesized with different binding capacities. The effect of the capacity on preconcentration, matrix elimination, and uptake capability at high flow rates was studied. For a high capacity IDA-Novarose (≥ 45 µmole/ml) quantitative uptake was seen even at high flow rates (100 ml/min) for Cu2+ with a high affinity to the adsorbent, and for Cd2+ with a moderate affinity. For lower capacities the uptake of Cd2+ was affected by the sample matrix and the flow rate. A method based on the determination of the conditional stability constant of the metal sorbent complex was suggested for the prediction of the sorbent capacity needed to obtain quantitative recovery and optimal matrix elimination. The sorbent was used in a flow system with online buffering for the analysis of a certified riverine water (SLRS-3), tap water and lake water. With few exceptions the results obtained by ICP-AES after preconcentration agreed well with the certified concentrations and results obtained by ICP-MS. The other sample preparation strategy discussed is a method for non digested biological samples from different animal organs for the multi element analysis by ICP-AES. This “mix and measure method” consists of a simple homogenization of the sample with a mixing rod in a small amount of neutral media, followed by dilution and direct measurement with ICP-AES. The total time of analysis is only a few minutes. The ability of this fast method to accurately quantify some elements of toxic, environmental, and/or physiological concern with the lowest possible sample dilution and the highest possible plasma load was evaluated. In 10 % liver slurry Cd, Co, and Sr, at concentration levels around 0.05 µg/g were quantified simultaneously with P and K around 2000 µg/g and with several other elements in between (Al, Ca, Cu, Fe, Mg, Mn, Pb, and Zn). The relative standard deviation of repeated measurements of samples was around 5 - 6 % for regardless of the concentration of the element. The method was also used for fast screening of the elemental distribution in mice organs (brain, heart, kidney, liver, lung and spleen).

Είναι ευρέως αποδεκτό ότι η ασφάλεια δεδομένων έχει ήδη ξεκινήσει να διαδραματίζει κεντρικό ρόλο στον σχεδιασμό μελλοντικών συστημάτων τεχνολογίας πληροφορίας (IT – Information Technology). Μέχρι πριν από λίγα χρόνια, ο υπολογιστής αποτελούσε την κινητήρια δύναμη της ψηφιακής επικοινωνίας. Πρόσφατα, ωστόσο, έχει γίνει μια μετατόπιση προς τις εφαρμογές τεχνολογίας πληροφορίας που υλοποιούνται σαν ενσωματωμένα συστήματα. Πολλές από αυτές τις εφαρμογές στηρίζονται σε μεγάλο βαθμό σε μηχανισμούς ασφαλείας, περιλαμβάνοντας την ασφάλειας για ασύρματα τηλέφωνα, φαξ, φορητούς υπολογιστές, συνδρομητική τηλεόραση, καθώς και συστήματα προστασίας από αντιγραφή για audio / video καταναλωτικά προϊόντα και ψηφιακούς κινηματογράφους. Το γεγονός ότι ένα μεγάλο μέρος των ενσωματωμένων εφαρμογών είναι ασύρματο, καθιστά το κανάλι επικοινωνίας ιδιαίτερα ευάλωτο και φέρνει στο προσκήνιο την ανάγκη για ακόμη μεγαλύτερη ασφάλεια. Παράλληλα με τα ενσωματωμένα συστήματα, η εκρηκτική ανάπτυξη των ψηφιακών επικοινωνιών έχει επιφέρει πρόσθετες προκλήσεις για την ασφάλεια. Εκατομμύρια ηλεκτρονικές συναλλαγές πραγματοποιούνται κάθε μέρα, και η ταχεία ανάπτυξη του ηλεκτρονικού εμπορίου κατέστησε την ασφάλεια ένα θέμα ζωτικής σημασίας για πολλές καταναλωτές. Πολύτιμες επιχειρηματικές ευκαιρίες , καθώς επίσης και πολλές υπηρεσίες πραγματοποιούνται κάθε μέρα μέσω του Διαδικτύου και πλήθος ευαίσθητων δεδομένων μεταφέρονται από ανασφαλή κανάλια επικοινωνίας σε όλο τον κόσμο. Η επιτακτική ανάγκη για την αντιμετώπιση αυτών των προβλημάτων, κατέστησε πολύ σημαντική την συμβολή της κρυπτογραφίας, και δημιούργησε μια πολύ υποσχόμενη λύση, με την οποία ενσωματωμένα συστήματα σε συνδυασμό με κρυπτογραφικά πρωτόκολλα, θα μπορούσαν να μας οδηγήσουν στην εξασφάλιση των επιθυμητών αποτελεσμάτων. Στην παρούσα εργασία, παρουσιάζουμε την υλοποίηση ενός ενσωματωμένου συστήματος, εμπλουτισμένο με κρυπτογραφικά πρωτόκολλα, που ουσιαστικά μεταμορφώνει έναν κοινό ηλεκτρονικό υπολογιστή σε ένα ισχυρό Crypto System PC, και έχει σαν κύρια αρμοδιότητα να μπορεί να επικοινωνεί με ένα υπολογιστικό σύστημα και να στέλνει πληροφορίες για την κατάσταση του μέσω ασφαλούς σύνδεσης διαδικτύου σε κάποιον απομακρυσμένο υπολογιστή ελέγχου/καταγραφής συμβάντων σε ώρες που δεν είναι εφικτή η παρουσία εξειδικευμένου προσωπικού για τον έλεγχο του. Αξιολογούμε την απόδοση του και την λειτουργία του με την εκτέλεση διάφορων πειραμάτων, ενώ επίσης προτείνουμε λύσεις για πιο ιδανικές και αποδοτικές συνθήκες λειτουργίας για μελλοντικές εφαρμογές. / It is widely recognized that data security already plays a central role in the design of future IT systems.Until a few years ago, the PC had been the major driver of the digital economy. Recently, however, there has been a shift towards IT applications realized as embedded systems.Many of those applications rely heavily on security mechanisms, including security for wireless phones, faxes, wireless computing, pay-TV, and copy protection schemes for audio/video consumer products and digital cinemas. Note that a large share of those embedded applications will be wireless, which makes the communication channel especially vulnerable and the need for security even more obvious. In addition to embedded devices, the explosive growth of digital communications also brings additional security challenges. Millions of electronic transactions are completed each day, and the rapid growth of eCommerce has made security a vital issue for many consumers. Valuable business opportunities are realized over the Internet and megabytes of sensitive data are transferred and moved over insecure communication channels around the world. The urgent need to face these problems has made the contribution of cryptography very important , and created a very promising solution, in which embedded systems in combination with cryptographic protocols, could lead us to obtain the desired results. In this paper, we present the implementation of an embedded system, enriched with cryptographic protocols, which turns a common computer into a powerful Crypto System PC, and has as its primary responsibility to be able to communicate with a computer system and send information for its situation through secure internet connections to a remote computer which is responsible for recording of events, when there is not qualified staff to control the computer system. We evalauate its performance and operation, by executing various experiments and we also suggest solutions for more optimal and efficient operating conditions for future applications.

Les attaques par canaux auxiliaires sont apparues dans la deuxième moitié des années 1990. Ces attaques exploitent différentes informations qu’il est possible de collecter lors de l’exécution d’un algorithme sur un appareil cryptographique. Il est ainsi possible, entre autres, de mesurer la consommation d’énergie d’un appareil cryptographique, ou encore d’observer le temps d’exécution d’un certain algorithme sur un appareil. C’est à ces deux sources d’in- formation que nous nous intéressons dans ce travail. Après une présentation des concepts utiles à la lecture du travail et de l’état de l’art des attaques et des contre-mesures du domaine, nous abordons les résultats de nos recherches effectuées lors de ce travail de thèse. Nous présentons d’abord nos contributions aux attaques par mesure de consommation d’énergie :(1) une approche com- binant apprentissage semi-supervisé et attaques par templates pour retrouver le poids de Hamming des différents bytes d’une clé de chiffrement et (2) une approche utilisant des techniques d’apprentissage automatique pour attaquer une implantation protégée d’AES. Ensuite, nous abordons les contre-mesures investiguées durant nos recherches qui se résument (1) en la possibilité de rendre l’ordre des instructions d’AES le plus aléatoire possible en jouant sur la relation de dépendance entre celles-ci ainsi qu’en (2) l’étude de l’application partielle (sur un sous-ensemble de données) de certaines contre-mesures, afin de protéger les données sensibles d’un algorithme. Enfin, nous terminons ce travail par l’emploi de la programmation orientée aspects comme manière d’implanter des contre-mesures pour les attaques temporelles (sur RSA) et pour les attaques par mesures de consommation d’énergie (sur AES). / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

With industry expectations of billions of Internet-connected things, commonly referred to as the IoT, we see a growing demand for high-performance on-chip bus architectures with the following attributes: small scale, low energy, high security, and highly configurable structures for integration, verification, and performance estimation. Our research thus mainly focuses on addressing these key problems and finding the balance among all these requirements that often work against each other. First of all, we proposed a low-cost and low-power System-on-Chips (SoCs) architecture (IBUS) that can frame data transfers differently. The IBUS protocol provides two novel transfer modes – the block and state modes, and is also backward compatible with the conventional linear mode. In order to evaluate the bus performance automatically and accurately, we also proposed an evaluation methodology based on the standard circuit design flow. Experimental results show that the IBUS based design uses the least hardware resource and reduces energy consumption to a half of an AMBA Advanced High-Performance Bus (AHB) and Advanced eXensible Interface (AXI). Additionally, the valid bandwidth of the IBUS based design is 2.3 and 1.6 times, respectively, compared with the AHB and AXI based implementations. As IoT advances, privacy and security issues become top tier concerns in addition to the high performance requirement of embedded chips. To leverage limited resources for tiny size chips and overhead cost for complex security mechanisms, we further proposed an advanced IBUS architecture to provide a structural support for the block-based AES algorithm. Our results show that the IBUS based AES-encrypted design costs less in terms of hardware resource and dynamic energy (60.2%), and achieves higher throughput (x1.6) compared with AXI. Effectively dealing with the automation in design and verification for mixed-signal integrated circuits is a critical problem, particularly when the bus architecture is new. Therefore, we further proposed a configurable and synthesizable IBUS design methodology. The flexible structure, together with bus wrappers, direct memory access (DMA), AES engine, memory controller, several mixed-signal verification intellectual properties (VIPs), and bus performance models (BPMs), forms the basic for integrated circuit design, allowing engineers to integrate application-specific modules and other peripherals to create complex SoCs.