The South African Global Navigation Satellite System (GNSS) network of dual frequency receivers provide an opportunity to investigate solar cycle effects on ionospheric Total Electron Content (TEC) over the South Africa region by taking advantage of the dispersive nature of the ionospheric medium. For this task, the global University of New Brunswick Ionospheric Modelling Technique (UNB-IMT) was adopted, modified and applied to compute TEC using data from the southern African GNSS Network. TEC values were compared with CODE International GNSS services TEC predictions and Ionosonde-derived TEC (ITEC) measurements to test and validate the UNB-IMT results over South Africa. It was found that the variation trends of GTEC and ITEC over all stations are in good agreement and show pronounced seasonal variations with high TEC values around equinoxes for a year near solar maximum and less pronounced around solar minimum. Signature TEC depletions and enhanced spikes were prevalently evident around equinoxes, particularly for a year near solar maximum. These observations were investigated and further discussed with an analysis of the midday Disturbance Storm Time (DST) index of geomagnetic activity. The residual GTEC – ITEC corresponding to plasmaspheric electron content and equivalent ionospheric foF2 and total slab thickness parameters were computed and comprehensively discussed. The results verified the use of UNB-IMT as one of the tools for ionospheric research over South Africa. The UNB-IMT algorithm was applied to investigate TEC variability during different epochs of solar cycle 23. The results were investigated and further discussed by analyzing the GOES 8 and 10 satellites X-ray flux (0.1 – 0.8 nm) and SOHO Solar Extreme Ultraviolet Monitor higher resolution data. Comparison of UNB-IMT TEC derived from collocated HRAO and HARB GNSS receivers was undertaken for the solar X17 and X9 flare events, which occurred on day 301, 2003 and day 339, 2006. It was found that there exist considerable TEC differences between the two collocated receivers with some evidence of solar cycle dependence. Furthermore, the daytime UNB TEC compared with the International Reference Ionosphere 2001 predicted TEC found both models to show a good agreement. The UNB-IMT TEC was further applied to investigate the capabilities of geodetic Very Long Baseline Interferometry (VLBI) derived TEC using the Vienna TEC Model for space weather monitoring over HartRAO during the CONT02 and CONT05 campaigns conducted during the years 2002 (near solar maximum) and 005 (near solar minimum). The results verified the use of geodetic VLBI as one of the possible instruments for monitoring space weather impacts on the ionosphere over South Africa.

Localized structures of the magnetic field strength depression are often observed in the interplanetarymedium, and they are called ‘magnetic holes’ after the original work of Turner et al. 1977. A numberof observations of similar features have been reported, while the mechanisms of their origin have notfully understood yet. The scale size of their structures varies from several to a few thousand of the protongyro radii, and their characteristic orientations of the magnetic field also vary, and therefore differenttypes of the magnetic holes have been suggested. To date, the magnetic holes are classified into Mirrormode and magnetic decreases (Tsurutani et al. 2011). Despite a large number of papers that report theobservational characteristics of the magnetic holes, many identify the feature using only the magneticfield data. This is due to the scale size of the structure at a large speed of the solar wind medium, thespatial resolution of the plasma instruments is often insufficient while the magnetic field instrument canusually obtain the data in high enough time resolution.The Cassini spacecraft orbited Saturn for almost 17 years and obtained a large amount of data in/near theKronian magnetosphere, where the series of the magnetic depletions have been also observed (Smith et al.1980). The Langmuir Probe (LP) onboard Cassini measures the spacecraft potential and, in turn, measuresthe electron density in in-situ in the outer magnetosphere and solar wind region. This measurement hasbeen done using the LP sweep mode which samples the current-voltage curve of the probe every 10 minin the outer magnetosphere. The LP has also been operated in the continuous mode that measures theprobe current at a fixed bias potential every 16 s allowing to calculate the electron density in a smallerscale that is required for the studies magnetic holes. However, there is no general calibration so far inorder to conduct a statistical study in the outer magnetosphere region. The goal of this project is toinvestigate the possibility to use the LP data for the magnetic hole study, calibrate the LP continuousmode to derive the plasma density near the magnetospheric of Saturn, and investigate the scale size of theplasma density structure in the magnetic holes, i. e. plasma β, the field strength and density.The calibration of the continuous data was done by finding a relation between the current at 11 V, whichis a typical bias voltage of continuous mode, and the spacecraft potential obtained by the LP the sweepmode data. Is is expected that the current at 11V is linearly proportional to the floating potential andtherefore can be used to derive the electron density with the potential and density relationship presentedby Morooka et al. 2009. I found that the spacecraft attitude against the sun has a strong effect on therelation, and derived 11V current-floating potential relationship depending on the different spacecraftattitude.Using the LP continuous data calibration above, I investigated the electron density characteristics aroundthe magnetic hold structure, and confirmed that they are generally in anticorrelation relationship. I estim-ated also the plasma β assuming a constant temperature of 100 eV and investigated their characteristicsfor the different types of magnetic holes (linear and rotational holes) both in the magnetosheath and theholes in the solar wind for the year 2011. For the Cassini dataset during 2011, various different shapeand sizes of magnetic hole events have been found. Most (80%) of the MHs appeared within a groupedstructure, while the rest (20%) are found as isolated type holes in the magnetosheath. Among the isolatedMHs, about 30% had "Gaussian shape" and about 40% had a substructure. The scale size for the electrondensity for the isolated holes were on average 50 s in the solar wind, and 75 s (the rotational holes) and120 s (the linear holes) in the magnetosheath. Therefore, I confirmed that the LP can obtain enough datapoints to resolve the magnetic holes structure in the magnetosheath. The Cassini LP data resolution isalso capable to resolve some of the magnetic hole structure in the solar wind.In summary, I confirmed that the Cassini LP continuous data calibrated in this study is capable toinvestigate the different types of magnetic hole structures. Using this calibrated electron data statisticallyfor the large number of Cassini orbit would helpful to further identify the MHs structures in the solar wind and the magnetosheath that can be a key to understand the generation mechanisms of the magneticholes. / Lokaliserade strukturer med låg magnetfältstyrkan ses ofta i interplanetära mediet och de kallas ’mag-netiska hål’ (MH) (Turner et al. 1977). Trots et antal observationer av sådana strukturer har observeratsär deras generationsmekanism ännu förstådd. Storleken av strukturerna varierar från ett fåtal till någratusen protongyroradier och även deras kännetecknande inriktningar i magnetfältet varierar. På grund avdetta har olika typer av MH förslagits. Idag klassificerar man MH som ’mirror mode’ och magnetiskaminskningar (Tsurutani et al. 2011). Många studier har undersökt de magnetiska hålens egenskaper,men tyvärr oftast baserats endast på magnetfältsdata. Detta kan bero på strukturernas storlek vid en storsolvindshastighet, där plasmainstrumenten oftast inte har tillräckligt hög tidsupplösning för mätningar,medan magnetfältsinstrumenten kan oftast tillhandahålla data i hög tidsupplösning.Cassini-rymdfarkosten kretsade runt Saturnus i nästan 17 år och erhöll stora mängder data i och näraSaturnus magnetosfär. Langmuir-sonden (LP) ombord Cassini mäter rymdfarkostens potential ochdärmed mäter den elektrontätheten i rymden. Instrumentet fungerar som en slags väderstation för rym-dplasma och möjliggör mätningen av fundamentala plasmaparametrar såsom elektrontäthet, jontäthet,elektrontemperatur och jonmassa i en tät plasmaområdet av nära Saturnus. I den yttre magnetosfären därden plasmatätheten är låg, kan LP mäta rymdfarkosts potential och plasmatätheten. Mätningen, så kallade’sweep mode’ kan skaffades var 10:e minuter. LP:en mäter också i ’kontinuerlig mode’ som möjligenkan mäta plasmatätheten i mer frekventa men den behöver allmän kalibrering. I detta projekt undersökerjag möjligheten att använda LP kontinuerlig data för att studera MH, skapa kalibraring funktion för’kontinuerlig mode’ för att uppskatta plasmatätheten i Saturnus magnetosfär, och även att undersökastorleken och karaktär av plasmatäthetenstrukturen i MH.Jag undersökte först relationen mellan LP ström vid 11V och rymdfarkostens potential i sweep mode data.De härledda funktionerna användes vidare för att uppskatta densiteten med användning av relationenmellan rymdfarkostens potential och elektrontätheten (Morooka et al. 2009). Jag upptäckte också attden kontinuerlig mode funktionen är olika beroende på LP sensors läge i förhållande till solen ochrymdfarkosten. Hur Cassini är inriktad har en stor effekt på relationen och därför beskriva jag fyra olikarelationer för olika inriktningsregioner. Med den kontinuerlig mode funktionen jag härlett, undersöktejag struktur av magnetiska hålen som har listats av Tomas Karlsson på KTH. År 2011 innehåller MH medmycket olika former och storlekar. Den mest (80%) MH identifierades som grupp och resten (20%) varsom isolerade MH i magnetosheath. Av dessa isolerande hål har ca. 30% en Gauss-form och nästan 40%av MH verkar ha en understruktur. Genom att jämföra magfältdatan med elektrontätheten bekräftadejag den allmänna antikorrelationen mellan magnetfältstyrkan och elektrontätheten i MH-strukturerna.Dessutom hittar jag en ökning av elektron β som beräknas med en temperatur av 100 eV för linjära ochroterade MH i den magnetosheath samt MH i solvinden under 2011. Storleken av de isolerade magnetiskahålen är i genomsnitt 50 s i solvinden, 75 s (roterade magnetiska hål) och 120 s (linjära magnetiska hålen)i magnetosheath:en. Därför kan Cassini LP ha tillräcklig många datapoäng för att upplösa struktur avMH i magnetosheath. I solvinden kan LP upplösa en del av relativt stora MH.Sammanfattningsvis kan LP:s kontinuerlig kalibreringen från detta projekt användas för att analyserade olika strukturerna och storlekar av MH. Med denna kalibrerade plasmatäthet data är det möjligt attidentifiera olika MH karaktär i statistiskt för det stora antalet Cassini data. Det skulle vara en stor hjälpför att förstå genereringsmekanismerna av de magnetiska hålen.

Several measurement campaigns took place at the ALOMAR observatory at Andøya, Northern Norway during July-November 2001 to validate ionospheric electron density and dry temperature profiles in the troposphere and lower stratosphere derived from radio occultation measurements of the low earth orbiter satellite CHAMP. For temperature sounding, three balloons are released around GPS satellite occultation events that occurred inbetween a distance of 200 km around Andøya. At altitudes of 7–20 km the CHAMP profile shows a positive mean deviation increasing with height by about 1.5-2 Kelvin/ 10 km overlayed with variations of ±1 K when compared to the radiosonde. Taking into account the previous and following radiosonde ascents the mean deviation seems to be of systematic nature due to the occultation principle or the retrieval algorithm and the variations are related to geographical variations of temperature and to the horizontal averaging by the radio occultation technique. During the period from mid July to mid August, four occultations for ionospheric soundings occurred. The values of the F2 layer calculated from the CHAMP derived electron density profiles are compared to the readings of the Alomar and Tromsø ionosondes for these times. Comparison shows that using the radio occultation technique electron densities of the maximum value layer are calculated inbetween the same order of magnitude as the ionosondes measurements, however, they overestimate it in the cases discussed here. / Zur Validierung von Elekronendichte- und Temperaturprofilen, abgeleitet aus Radiookkultationsmessungen von CHAMP wurden im Juli-November 2001 mehrere Messkampagnen am ALOMAR Institut auf Andøya, Nordnorwegen durchgeführt. Zur Temperatursondierung wurden drei aufeinanderfolgende Radiosonden um den Zeitpunkt von Okkultationsereignissen im Umkreis von weniger als 200 km gestartet. Das hier diskutierte Temperaturprofil von CHAMP zeigt im Höhenbereich 7-20 km eine mit der Höhe zunehmende positive Abweichung von ca. 1,5-2 K/10 km mit Variationen um ±1 K verglichen mit dem Temperaturprofil der zum Okkultationszeitpunkt fliegenden Radiosonde. Der Vergleich mit den vorhergehenden und nachfolgenden Sondierungen lässt darauf schließen, dass die mittlere Abweichung durch systematische Fehler des Okkultationsverfahrens oder den Retrieval-Algorithmus bedingt sind, die Variationen jedoch durch die örtliche Abweichung und die horizontale Mittelung des Messverfahrens. Während des Zeitraumes von Mitte Juli bis Mitte August ereigneten sich vier Okkultationen zur Sondierung der Ionosphäre. Von den abgeleiteten Elektronendichteprofilen werden jeweils die Werte der F2-Schicht mit den zur gleichen Zeit gemessenen Elektronendichten der Ionosonden auf Andøya und bei Tromsø verglichen. Der Vergleich zeigt, dass mit Hilfe der Radiookkultaktionstechnik die Elektronendichtewerte der F2-Schicht in der gleichen Größenordnung berechnet, in diesen konkreten Fällen jedoch überschätzt werden.

GPS integrated Total Electron Content measurements received at the ground or in space are used for tomographic reconstruction of the ionospheric electron density distribution. The IRI/GCPM model is used as initialisation of the tomographic MART algorithm. During the procedure GPS TEC data are iteratively assimilated to the model. To test the potential of the reconstruction, electron density profiles from IRI/GCPM and the assimilation are compared with ionosonde measurements and CHAMP radio occultation profiles for dates during the HIRAC campaign in April 2001. All profiling methods show electron density values of similar magnitude. It is shown that including TEC GPS data corrects the model towards the ionosonde measurements. / Integrale Messungen der Elektronendichte aus GPS-Boden- sowie Radio-Okkultations-Messungen bilden die Datenbasis der hier vorgestellten 3-dimensionalen Tomographie der ionosphärischen Elektronendichteverteilung. Zur Initialisierung des verwendeten iterativen MART Algorithmus wird das IRI/GCPM Modell verwendet, wobei das Modell während der Iteration sukzessiv an die Messdaten angepasst wird. Um das Potential des Verfahrens abzuschätzen, werden Elektronendichteprofile des IRI/GCPM Modells und der Rekonstruktion mit Ionosondenmessungen und CHAMP Okkultationsprofilen verglichen. Dafür wurden Messungen während der HIRAC Kampagne im April 2001 genutzt. Alle hier gezeigten Profilableitungen geben Elektronendichtewerte der selben Größe wieder. Eine Annäherung des IRI/GCPM Modells an die Messwerte der Ionosonde durch die Assimilation der TEC GPS Daten wird gezeigt.

The ionospheric peak electron density NmF2, simulated with the Coupled Thermosphere Ionosphere Plasmasphere electrodynamics (CTIPe) model was used to study the ionospheric response to solar flux in years of low (2008) and high (2013) solar activity. The CTIPe NmF2 was compared to the Whole Atmosphere Community Climate Model with Thermosphere and Ionosphere Extension (WACCM-X) and the Constellation Observing System for Meteorology, Ionosphere, and Climate (COSMIC) NmF2 in March and July of 2008 and 2013. The comparison shows that the CTIPe NmF2 is lower than the COSMIC andWACCM-X NmF2. Both models successfully reproduce the semi-annual variations seen in the COSMIC observations. Analysis of the 27-day variations of the CTIPe NmF2 shows that the midnight NmF2 deviations are stronger than the midday deviations. In addition, at low solar activity, the 27-day variations of NmF2 are larger in the Southern Hemisphere, while at high solar activity, the 27-day variations of NmF2 are larger at the equator and in the Northern Hemisphere. An ionospheric delay was estimated with CTIPe simulated NmF2 at the 27-day solar rotation period during low and high solar activity. During low (high) solar activity, an ionospheric delay of about 12 (34) hours is predicted indicating an increasing ionospheric delay with solar activity. / Die maximale ionosphärische Elektronendichte NmF2, die mit dem Coupled Thermosphere Ionosphere Plasmasphere electrodynamics (CTIPe) Modell simuliert wurde, wurde zur Untersuchung der ionosphärischen Reaktion in Jahren mit geringer (2008) und hoher (2013) Sonnenaktivität verwendet. CTIPe vorhergesagte NmF2 wurde mit derjenigen des Whole Atmosphere Community Climate Model with Thermosphere and Ionosphere Extension (WACCM-X) und Messwerten des Constellation Observing System for Meteorology, Ionosphere, and Climate (COSMIC) im März und Juli der Jahre 2008 und 2013 verglichen. Der Vergleich zeigt, dass NmF2 aus CTIPe geringer ist als das COSMIC gemessene und von WACCM-X simulierte. Beide Modelle reproduzieren erfolgreich die von COSMIC beobachteten halbjährlichen Schwankungen. Die Analyse der 27-tägigen Schwankungen des CTIPe NmF2 zeigt, dass die mitternächtlichen NMF2-Abweichungen stärker sind als diejenigen am Mittag. Außerdem sind bei geringer Sonnenaktivität die 27-Tage-Abweichungen von NmF2 in der Südhemisphäre größer, während bei hoher Sonnenaktivität die 27-Tage-Abweichungen von NmF2 am Äquator und in der Nordhemisphäre größer sind. Die ionosphärische Verzögerung während geringer und hoher Sonnenaktivität wurde für die 27-tägige Sonnenrotation mit CTIPe simuliert. Bei geringer (hoher) Sonnenaktivität wird eine ionosphärische Verzögerung von etwa 12 (34) Stunden beobachtet, was auf eine zunehmende ionosphärische Verzögerung mit zunehmender Sonnenaktivität hinweist.

Intermetallic borides are characterized by a great variety of crystal structures and bonding interactions, however, a comprehensive rationalisation of the electronic structure is missing. A more general interpretation will be targeted towards comparing several boride phases of one particular transition metal on one hand side, but also isostructural borides of various metals at the other side. Finally, a concise model should result from a detailed analysis of excellent data both from experimental charge density analysis and quantum chemical methods. Ultimate target is a transferability model based on typical building blocks. Experimental investigations of the electron density derived from diffraction data are very rare for intermetallic compounds. One of the main reasons is that the suitability of such compounds for charge density analysis is estimated to be relatively low as compared to organic compounds. In the present work, X-ray single crystal diffraction measurements up to high resolution were carried out for TiB2, VB2, V3B4, and VB crystals. The respective experimental electron densities were reconstructed using the multipole model introduced by Hansen and Coppens [1]. The topological aspects of the experimental electron density were analysed on the basis of the multipole parameters using Bader’s Quantum Theory, Atoms in Molecules [2] and compared with theoretical calculations. References [1] Hansen, N.K.; Coppens, P. Acta Crystallogr. 1978, A34, 909 [2] Bader, R.F.W. Atoms in Molecules─A Quantum Theory; Oxford University Press: Oxford, 1990

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第24975号 / エネ博第471号 / 新制||エネ||88(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー変換科学専攻 / (主査)教授 長﨑 百伸, 教授 田中 仁, 教授 稲垣 滋 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

Alloy nanoparticles have been extensively studied for decades. However, the synthesis and characterization of alloy nanoparticles are still posing significant challenges, leading to an increasing demand for in situ characterization techniques. Small-angle X-ray scattering (SAXS) is a powerful method for structural analysis of nanoparticles. As the SAXS signal is essentially the Fourier transform of the electron distribution, it provides structural information for the entire ensemble of nanoparticles. The development of SAXS has been facilitated by significant advances in synchrotron X-ray sources and data processing methods, leading to the development of the 3D-SAXS method, which enables the reconstruction of the 3D structures of particles from SAXS profiles.Although SAXS has the potential to be a powerful tool for investigating the internal structures of alloy nanoparticles, its application is hindered by the challenges posed by polydispersity, which can cause smearing effects that complicate the geometry recovery process. This dissertation presents a novel approach to overcome the problem of polydispersity in SAXS data analysis, thus demonstrating the utility of SAXS in investigating the internal electron density distributions of alloy nanoparticles. In Chapter 2, the SharPy algorithm is introduced as a size-refocusing program that reduces the smearing effect caused by polydispersity in SAXS data. SharPy is based on a penalized iterative regression approach to fit the pair distance distribution function (PDDF) with an estimated size distribution. It can provide detailed information about the shape of nanoparticles from the smeared SAXS signal under various scenarios and conditions. Chapter 3 investigates the simulated SAXS profiles of AuAg core-shell nanoparticles with varying size distribution, core-shell ratio, and degrees of alloying. It demonstrates the capability of SAXS in observing the electron density distribution of AuAg core-shell structures. These findings provide insights into the potential of SAXS as a reliable method for investigating the internal structures of alloy nanoparticles. Chapter 4 focuses on synthesizing and characterizing AuAg nanoparticles. Their SAXS profiles and PDDF analysis demonstrate that SAXS can distinguish between homogeneous and core-shell nanoparticle structures. In this chapter, the SharPy algorithm is first-time applied to real experimental data, demonstrating its ability to reveal the core-shell structure from a polydisperse nanoparticle system. Chapter 5 investigates the evolution of alloying AuAg nanoparticles through a combination of SAXS/PDDF analysis, 3D reconstruction, and molecular dynamics (MD) simulation. The study presents the 3D electron density distribution of alloying AuAg nanoparticles. The 3D reconstruction with electron density mapping provides a straightforward visualization of the electron density distribution pattern of the alloying AuAg nanoparticles. The success of the SAXS experiment lies in the development of the 3D-SAXS pipeline, which involves the use of SharPy and 3D reconstruction programs, making 3D SAXS a promising alternative to electron microscopy for visualizing the morphology of nanoparticle systems. / Chemistry

"We cannot afford the luxury any longer of ignoring the nature of the bonding in these interesting compounds .... " P.E.D. Morgan, (1974). An understanding of bonding is paramount to furthering our understanding of materials (Morgan, 1974). The properties of materials are governed by the interactions between atoms. These interactions are governed by the nature of the bonds. In this study, two methods are explored which provide insight into chemical interactions. First, promolecule radii, calculated for nitride, oxide, and sulfide coordinated polyhedra with bond lengths fixed at the sums of effective ionic and crystal radii, are analyzed. Radii calculated for transition and non-transition cations for the first four rows of the periodic table are highly correlated with crystal radii derived for oxide and sulfide crystals and with ionic radii derived for nitride crystals. Promolecule radii calculated for the coordination polyhedra match experimentally determined bonded radii to within ~0.02Å, on average. Calculated radii anions tend to match ionic radii when bonded to highly electropositive cations and atomic radii when bonded to highly electronegative cations. In the second study, molecular orbital calculations were completed on a series of small molecules containing the nitride anion. Bond type can be characterized by studying the systematics of parameters derived from the bond critical point properties of the electron density distributions. A set of criteria is established to suggest how covalent or ionic a bond is. This criteria is based on bond critical point properties such as the Laplacian of the electron density distribution evaluated at the bond critical point, the electron density distribution at the critical point, the local energy density at the critical point, the relative electronegativity of the cation, the curvatures of the electron density distribution, and the distance from the nucleus of the nitride anion to the bond critical point, (the bonded radius of the nitrogen atom). Parameters computed for promolecule data indicate that these easily obtained results offer a method of calculating bond critical properties which are close in value to the more extensive results derived from molecular orbital calculations. / Ph. D.

La miniaturisation des composants CMOS (Complementary Metal Oxide Semiconductor) impose l’emploi de matériaux diélectriques de permittivité élevée. LaAlO3 et SrTiO3 sont aujourd’hui parmi les meilleurs candidats ; toutefois, la diffusion de l’oxygène dans ces matériaux conduit à la dégradation des propriétés électriques et de l’interface avec le silicium. Ce travail théorique a pour but d’étudier les facteurs gouvernant, à l’échelle de la liaison chimique, la diffusion de l’ion oxygène. L’approche choisie repose sur la théorie de la fonctionnelle de la densité (DFT), couplée à des méthodes d’analyse de la densité électronique, et sur le développement d’un outil original : les cartes de densité d’énergie. Les régions de la densité électronique contribuant à la barrière de diffusion ont ainsi pu être identifiées; une optimisation de ces matériaux à l’échelle de la liaison chimique peut alors être envisagée. / The miniaturization of CMOS (Complementary Metal Oxide Semiconductor) components requires the use of high dielectric permittivity materials as gate oxide. LaAlO3 and SrTiO3 are among the best candidates, but the oxygen diffusion in these materials leads to the degradation of both the electrical properties and the interface with silicon. In this context, the aim of this theoretical work is to study the factors governing the oxygen ion diffusion at the chemical bonding scale. This approach is based on Density Functional Theory (DFT), coupled with electron density analysis methods, and the pioneering development of energy density cards. The regions of the electron density contributing to the diffusion barrier have been identified allowing new routes of optimization of these materials across the chemical bonding.