This portfolio of work contributes to the remit of the National Physical Laboratory (NPL) to develop the underpinning expertise and tools for validating nascent and future optical quantum technologies based on the discrete and quantum properties of photons. This requirement overlaps with the requirement to provide validation for devices operating in the photon-counting regime. A common theme running through the portfolio is photon pairs generated through spontaneous parametric downconversion (SPDC). A Hong-Ou-Mandel (HOM) interferometer sourced with visible wavelength photon pairs from an SPDC process in beta-barium borate (BBO) was designed, built and characterised. The visibility of the HOM interference is dependent on the indistinguishability of the interfering photons, but is also influenced by imperfections of the interferometer; therefore an investigation was carried out to quantify the effects of the interferometer imperfections on the measured visibility so that the true photon indistinguishability could be measured with a quantified uncertainty. A bright source of correlated pair photons in the telecoms band based upon a pump enhanced SPDC process in periodically-poled potassium titanyl phosphate (PPKTP) was designed, built and characterised. From the characterisation measurements the source brightness was estimated to be 6.2×10⁴ pairs/ s/ mw pump. The photon pairs were further characterised through their incorporation as a source in a HOM interference experiment. The developed correlated photon pair source was at the heart of a novel scheme for the generation of polarisation entangled photon pairs, for which the design, build and characterisation work is presented. The source was demonstrated to produce two of the four maximally entangled Bell states with quantum interference visibilities of around 0.95. The generated states were also shown to break a form of Bell's inequality by around six standard deviations. The polarisation entangled photon pair source was originally built at the University of St Andrews and was later transferred to the NPL where it will extend NPL's capabilities to this key spectral region. Finally a study was carried out to investigate the possibility of a wavelength tuneable device for the absolute measurement of single photon detector quantum efficiencies based upon an established SPDC technique.

Le but de cette thèse est de développer des sources d’intrication photonique en vue d'applications en sciences information quantique. Dans ce contexte, nous présentons une source très performante et entièrement guidée permettant, au moyen d'une boucle de Sagnac, la génération d'états hyper-intriqués en polarisation et en énergie-temps. La configuration guidée rend le dispositif versatile, efficace et compatible avec une large bande spectrale, répondant ainsi au besoin des systèmes et réseaux de communication fibrés. À cette fin, nous avons distribué simultanément dans différents canaux télécoms des paires de photons hyper-intriqués au moyen de multiplexeurs en longueur d'onde à 5 canaux (DWDM), augmentant de fait le débit. La qualité de l'intrication est validée par la violation d'une inégalité de Bell étendue à un espace de Hilbert à 16 dimensions. Afin de pouvoir interfacer des photons aux longueurs d'ondes des télécommunications avec les bandes d'absorption des mémoires quantiques situées dans le visible, nous avons également développé une interface cohérente en longueur d'ondes. Un nouveau dispositif de métrologie quantique permettant la mesure avec une précision inégalée des effets de la dispersion chromatique dans les fibres optiques standards est également proposé. Notre approche "quantique" améliore la précision par un facteur 2.6 par rapport aux méthodes de mesures conventionnelles. Dans ce même contexte, nous avons aussi implémenté un nouveau protocole de métrologie de la phase de deux photons en ne détectant uniquement qu'un seul photon. Cette réalisation ouvre la voie à des applications potentielles simples s'appuyant sur peu de ressources au niveau de la détection. Finalement, dans la perspective de la miniaturisation de dispositifs quantiques, nous avons démontré un générateur d'intrication annoncée intégré sur puce qui trouve des applications en calcul et métrologie quantique. / The aim of this thesis was to develop photonic entanglement sources and study their implementation in the general field of quantum information technologies. To this end, a novel fully wave-guided, high performance photonic entanglement source is presented, able to generate hyper-entangled states in the observables of polarization and energy-time by means of a nonlinear Sagnac loop. The waveguide-based design makes it flexible, reliable, and adaptable to a wide spectral range, paving the way towards compact photonic entanglement generators, compatible with fiber-based communication systems and networks. This has been underlined by generating and distributing hyperentanglement in 5x2 dense wavelength division multiplexed channel telecom pairs, simultaneously, towards higher bit rates. The quality of the generated entanglement has been qualified by violating the Bell inequalities in a 16-dimension Hilbert space. Moreover, to adapt the wavelength of the entangled telecom photon pairs to the absorption wavelength of current quantum memory systems, a coherent wavelength converter is demonstrated. Furthermore, within the framework of quantum metrology, a new concept for a high-precision chromatic dispersion (CD) measurement in standard single mode fibers is introduced and demonstrated. In this demonstration, due to conceptual advantages enabled by quantum optics, an unprecedented 2.6 times higher accuracy on CD measurements is shown, compared to state-of-the-art techniques. In the same context, a new protocol for measuring two-photon phase shifts is performed using single photon detection only, promising scalable and potential real device applications with limited resources and simplified detection schemes. Finally, any potential application of quantum optics will be realized using small-scale devices. In this framework, an integrated on-chip heralded path entanglement generator is demonstrated, and shown to be adaptable to logic gate operations.

Cette thèse rapporte les mesures de transport réalisées sur des jonctions moléculaires à l'état solide large échelle, mettant en évidence des effets d'interférence quantique. Le premier chapitre pose les bases théoriques de ce phénomène et introduit le formalisme des fonctions de green hors équilibre adapté à la description du couplage molécules/interfaces métalliques. Le second chapitre présente l'état de l'art expérimental dans ce domaine et résume les principales expériences ayant permis de mettre en évidence des effets d'interférences à l'échelle moléculaire. Le troisième chapitre décrit les étapes de fabrication mises en place pour construire les dispositifs mesures pendant ce travail de thèse. Les résultats expérimentaux obtenus sur les mesures de conductance des jonctions moléculaires sont décrits dans le quatrième chapitre et compares a plusieurs modèles théoriques qui confirme la présence d'interférences quantiques. Le dernier chapitre aborde les effets de thermoélectricité qui peuvent avoir lieu dans ces jonctions en présence d'interférence / This thesis reports the transport measurement performed on large scale solid state molecular junctions, highlighting quantum interference effect. First chapter set the theoretical basis of such a phenomenon and introduces the out of equilibrium green's functions formalism which is adapted to the description of coupling molecules/metallic interfaces. Second chapter presents the corresponding experimental state of the art and summarizes the experiments that have contributed to highlight interference effect at the molecular scale. Third chapter describes the fabrication steps optimized to build the devices measured during the thesis work. Experimental results obtained on conductance measurements are described and compared to several theoretical models that confirm the presence of quantum interference. Last chapter deals with thermoelectric effect that can occur in presence of interference

Thesis (MScEng (Electrical and Electronic Engineering))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: Assessing the quality of fruit has become vitally important for farmers and growers. With retailers placing ever stricter requirements on fresh produce, growers have to spend a greater amount of time and effort sorting and grading their harvest. Increasingly, vendors are placing requirements not only on external factors like colour, and firmness, but on internal quality factors such as sugar content and acidity, because, although consumers buy fruit based on their external appearances, the taste of the fruit is what determines whether the consumer will buy again. Different techniques exist that probe the internal quality of fruit non-destructively. The technique most widely used today is Near Infrared Spectroscopy. This technique is powerful, but has certain limitations such as poor reliability and the need for constant recalibration. This thesis suggests an alternative method for evaluating internal fruit quality based on low-field nuclear magnetic resonance detected by superconducting quantum interference devices. It introduces the theory of SQUIDs and NMR, and evaluates the use of SQUID detected NMR spectroscopy as a method for determining the internal quality of fruit. The fabrication techniques and processes are explained in detail and a design for a SQUID detected NMR spectrometer is given. Relevant simulations and simulation results are also given. No working SQUID could be fabricated and, as such, no working NMR spectrometer was demonstrated. This thesis serves as a reference work for future research. / AFRIKAANSE OPSOMMING: Bepaling van die gehalte van vrugte het vir boere uiters belangrik geword. Met kleinhandelaars wat al strenger vereistes plaas op vars produkte moet boere meer tyd en inspanning bestee met die sortering en gradering van hul oes. Handelaars plaas nie net vereistes op eksterne kwaliteitsfaktore soos kleur en fermheid nie, maar begin al hoe strenger vereistes plaas op interne kwaliteitsfaktore soos suikerinhoud en suurgehalte, want, hoewel verbruikers vrugte koop op grond van hul eksterne kwaliteitsfaktore, is dit die smaak van die vrug wat bepaal of die verbruiker weer die vrug sal koop. Verskillende tegnieke bestaan wat die interne kwaliteit van vrugte op ’n nie-destruktiewe manier kan bepaal. Die mees algemene tegniek is Naby Infrarooi Spektroskopie. Hierdie tegniek is kragtig maar het sekere beperkings soos swak betroubaarheid en die noodsaaklikheid van konstante herkalibrasie. Hierdie tesis stel ’n alternatiewe metode vir die evaluering van interne vrugkwaliteit gebaseer op lae-veld kernmagnetiese resonans waargeneem deur supergeleidende kwantum inmenging toestelle voor. Dit stel die teorie van SKWITs en KMR bekend, en evalueer die gebruik van SKWIT-bespeurde KMR spektroskopie as ’n metode vir die bepaling van die interne kwaliteit van vrugte. Die fabrikasie tegnieke en prosesse word in detail verduidelik en ’n ontwerp vir ’n SWKIT opgevangde KMR spektrometer word gegee. Toepaslike simulasies en simulasie resultate word ook gegee. Geen werkende SKWIT kon vervaardig word nie en as gevolg daarvan kon geen werkende KMR spektrometer gedemonstreer word nie. Hierdie tesis dien as ’n naslaan werk vir toekomstige navorsing.

Orientador: Guillermo Gerardo Cabrera Oyarzun / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Abstract: Quantum spin systems are caracterized by huge spaces of states, whose dimensions grow exponentially with the particles number. If following the preparation of the initial state, the system is kept isolated from external variables, it will develop a unitary time evolution according to Schrödinger equation or to Liouville equation. The system is driven exclusively by quantum uctuations, whose origin is the Uncertainty Principle. The evolution of a quantum state or a physical observable or mathematical nonobservable operator mean values may involve all states of the whole space of states, or big or small fractions of the total number of states. The analysis of the relaxation of a spin system from an arbitrary initial state to the equilibrium has to cope in general with the difficulty of requiring an extraordinarily great number of eigenstates and eigenvalues. In this work the main interest is centered on the evolution of magnetization¿s Fourier components in low dimensional systems of spins 1/2, whose interactions be given by the exchange modeled by Heisenberg Hamiltonians with axial anisotopy, XXZ. Exact solutions, analitic or numeric, are obtained. This is the continuation of work done in our research group which dealt with XY Hamiltonian families. In the analysis of the systems with the Hamiltonian XXZ, it was specially analysed the subspace defined by null total magnetization and the subspace defined by one spin wave, where chains up to 14 and 1200 were treated, respectively. There are emergence of fast and slow relaxation processes, which depend on the interations and on the initial state, and which result from destructive or constructive quantum interferences. Connections between the presence of those processes and the energy spectrum structure is discussed. Finally, the time evolution of some measures of global entanglement from initial states in the subspace of one spin wave are analised: the considered dynamics creates global entanglement until each entanglement measure reaches a saturation / Made available in DSpace on 2018-09-24T18:24:44Z (GMT). No. of bitstreams: 1 Carvalho_JulioGarcia_D.pdf: 5851086 bytes, checksum: fe9467d4e143df319d98e75ddb334401 (MD5) Previous issue date: 2006 / Resumo: Os sistemas quânticos de spin são caracterizados por espaços de estados muito grandes, cujas dimensões crescem exponencialmente com o número de partículas. Se após a preparação do estado inicial, o sistema for mantido isolado de variáveis externas, desenvolve-se uma evolução temporal unitária prescrita pela equação de Schrödinger ou pela equação de Liouville. O sistema é movido exclusivamente por flutuações quânticas, as quais têm sua origem no Princípio da Incerteza. A evolução de um estado quântico ou de valores médios de observáveis físicos ou de operadores matemáticos não observáveis pode envolver todos os estados do espaço de estados, ou frações grandes ou pequenas do número total de estados. A análise da relaxação de um sistema de spins desde um estado inicial arbitrário até o equilíbrio apresenta a dificuldade de requerer em geral um número extraordinariamente grande de auto-estados e autovalores. Neste trabalho o maior interesse está na evolução das componentes de Fourier da magnetização em sistemas de baixa dimensão espacial, com spins 1/2 e cujas interações sejam dadas pela troca modelada por Hamiltonianos de Heisenberg com anisotropia axial, XXZ. Serão obtidas soluções exatas: numéricas ou analíticas. A motivação proveio de trabalhos anteriores realizados no grupo de pesquisa referentes a famílias do Hamiltoniano XY. Ao se considerar o Hamiltoniano XXZ, analisou-se especialmente o subespaço definido por magnetização total nula e o subespa¸ co de uma onda de spin, onde trataram-se cadeias com até 14 e 1200 sítios, respectivamente. Há emergência de processos rápidos e lentos de relaxação, os quais dependem das interações e do estado inicial, e resultam de interferência quântica destrutiva ou construtiva. Serão discutidas conexões entre a presença desses processos e a estrutura do espectro de energia. Finalmente serão analisadas as evoluções temporais de algumas medidas de emaranhamento global, a partir de estados contidos no subespaço de uma onda de spin: a dinâmica considerada cria emaranhamento global até cada medida atingir uma saturação / Doutorado / Física da Matéria Condensada / Doutor em Ciências

Thesis(MScEng)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: The SQUID-NMR technique has been increasingly recommended by many researchers as holding a lot of potential, and it is believed it will become an invaluable tool for non-destructive evaluation in the future. Most of its potential is yet to be exploited. Non-destructive quality control of food products is one of the applications where such a system is being tried. Much of the progress that has been made in improving such a system to the present degree of user friendliness and cost effectiveness shows that, with more effort, it would be possible to implement the technology for on-line sorting, and possibly to reduce it down to hand-held devices. The goal was to investigate the feasibility of the internal fruit quality measurements using the NMR technique, and to develop a SQUID system suitable for SQUID-NMR application, intended for a later integration in a full SQUID-NMR system. A working dc SQUID was manufactured on an YBCO (Y Ba2Cu3O7􀀀 ) thin film deposited on a 10 mm x 10 mm MgO substrate. The SQUID was made of microbridge Josephson junctions, patterned by using the double resist laser lithography method, implemented during the course of this manufacturing process. The test of the SQUID showed a non-hysteretic current-voltage characteristic. Under the action of bringing a magnet closer to the SQUID under test, and then retracting it, the modulation of the I-V curve was observed. The critical current of the SQUID was 20 A and the resistance was 5.5 A series of experiments were performed on destructive measurements of the sugar content in table grapes using NMR, in order to evaluate the feasibility of this technique. The total sugars(TSS) measurements of the same samples were carried out by refractometry, chosen as a conventional method for validation. The NMR measurements were evaluated to be 5.4% precise and have an accuracy of 9.3% relative to the refractometry measurements. A further series of experiments were carried out on a high-Tc SQUID-NMR system. A high correlation coefficient (0.85) of the increasing values of the T1 and T2 relaxation times to the decreasing concentration of sugar (sucrose) in water was obtained. Non-destructive measurements T1 and T2 in table grapes suggested a possible prediction of sugar content in table grapes from the values of T1 or T2. This technique also presented many advantages compared to the conventional high field NMR technique, such as the fast measurements that do not require spectral processing, the ease of sample preparation, and its non-destructive nature. / AFRIKAANSE OPSOMMING: Die SQUID-NMR tegniek word al hoe meer aanbeveel deur navorsers oor die groot potensiaal, en dit beloof om in die toekoms van onskatbare waarde te wees in nie vernietigende evaluering. Die potensiaal moet grotendeels nog ontgin word, en die nie vernietigende kwaliteitsbeheer van voedselprodukte is een van die toepassings wat hier getoets word. Die vooruitgang tot dusver om die stelsel te verbeter wat die gebruikersvriendelikheid en koste-effektiwiteit betref, toon dat met effens meer moeite dit moontlik sal wees om die tegnologie aan te pas vir lynsortering van vrugte, en om dit dalk ook as handtoestel beskikbaar te stel. Die vooruitgang tot dusver om die stelsel te verbeter wat die gebruikersvriendelikheid en koste-effektiwiteit betref, toon dat met effens meer moeite dit moontlik sal wees om die tegnologie aan te pas vir lynsortering van vrugte, en om dit dalk ook as handtoestel beskikbaar te stel. Die doel is om die uitvoerbaarheid van interne vrugtekwaliteit metings deur hierdie tegniek te ondersoek en om ’n SQUID stelsel te ontwikkel wat gepas is vir SQUIDNMR toepassing, met die doel om dit later in ’n volledige SQUID-NMR stelsel te kan integreer. ’n Werkende GS-SQUID is vervaardig op ’n YBCO dunfilm wat op ’n 10 mm x 10 mm MgO substraat gedeponeer is. Die SQUID is van mikro-brug Josephson aansluitings/ voegvlakke, waarop in die loop van die vervaardigingsproses ’n patroon m et dubbelweerstand laser litografie neergelê is. Toets van die SQUID het ’n niehisterese stroom-spanning as kenmerkend getoon. Die nader bring en terugtrekking van ’n magneet het gelei tot waarneming van die modulasie van die I-V kurwe. Die kritieke stroom van die SQUID was 20 A en die weerstand was 5.5 ohm. ’n Reeks eksperimente is uitgevoer oor vernietigende metings van die suikerinhoud van tafeldruiwe met gebruik van NMR, om die gangbaarheid van hierdie tegniek te evalueer. Totale suikers (TSS) metings van dieselfde monsters is uitgevoer deur refraktometrie, wat gekies is as gebruiklike metode vir geldigheidsbepaling. Die NMR metings is as 5.4% presies/noukeurig evalueer, en met ’n akkuraatheid van 9.3% teenoor die refraktometrie metingsyfers. ’n Verdere reeks eksperimente is uitgevoer op ’n hoë-Tc SQID-NMR stelsel. ’n Hoë korrelasiekoëffisiënt van 0.85 van die toenemende waardes van T1 en T2 ontspantye teenoor die afname in konsentrasie van sukrose in water is waargeneem. Nie-vernietigende metings van T1 eb T2 in tafeldruiwe het gelei tot die moontlikheid van gebruik van hierdie tegniek om suikerinhoud van tafeldruiwe te voorspel. Die tegniek het ook baie voordele getoon in teenstelling met die gebruiklike hoëveld NMR tegniek, onder andere dat hierdie metings vinniger is, nie verdere verwerking van die spektrum benodig nie, die maklike voorbereiding van die monsters en die nie-vernietigende aard van die proses.

Thesis (MScEng)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: Geomagnetic storms are primarily driven by the rapid transfer of energy from the solar wind to the magnetosphere. The mechanism of energy transfer involves the merging of the interplanetary magnetic field to the geomagnetic field in a process known as magnetic reconnection. This leads to an influx of energetic, charged particles into the magnetosphere so that current systems are enhanced. Specifically, an increase in the equatorial ring current leads to a decrease in the surface field. Geomagnetic storms are thus characterized by a strong decline in the horizontal components of the geomagnetic field, lasting from several hours to days. The intensity of a storm is described by the disturbed storm-time index, which is essentially a measure of the deviation from the typical quiet day variation along the equator. Severe storms can lead to the disruption of high frequency (HF) communications as a consequence of a strongly perturbed ionosphere. By the same token, the global positioning system (GPS) can become highly unreliable during magnetically disturbed conditions, yielding distance errors as large as 50 meters. The impact of geomagnetic activity and other solar-driven processes on technology systems are collectively known as space weather. Magnetic field sensing thus forms an important part of space weather forecasting and is vital to space science research as a means of improving our understanding of solar wind-magnetosphere interactions. This study examines the use of magnetometers built as SQUIDs (Superconducting Quantum Interference Devices) for monitoring the geomagnetic field for space weather forecasting purposes. A basic theory of superconductivity is presented and subsequently the key aspects governing the operation of SQUIDs are discussed. Space weather is also introduced with respect to the various processes on the sun that perturb the magnetosphere and hence the geomagnetic field. The method of analysis was basically to Fourier-transform the data using the Wiener-Khintchine theorem. A systematic approach to Fourier analysis is thus presented, demonstrating the superiority of the Wiener-Khintchine theorem in noise reduction. The suitability of SQUID magnetometers for space science research is demonstrated by a comparative study between SQUID and fluxgate datasets for magnetic storms during 2011. Strong correlation was observed between the frequency content of the SQUID and fluxgate signals. This result supports South Africa’s SQUID project, currently undertaken as a collaborative effort between SANSA Space Science and the Department of Electrical and Electronic Engineering at Stellenbosch University. This thesis thus lays a foundation for future research involving advanced magnetometry using SQUIDs. / AFRIKAANSE OPSOMMING: Geomagnetiese storms word hoofsaaklik gedryf deur die vinnige oordrag van energie van die sonwind na die magnetosfeer. Die meganisme van energie oordrag behels die samesmelting van die interplanetêre magneetveld met die geomagneetveld, in 'n proses wat bekend staan as magnetiese heraansluiting. Dit lei tot 'n instroming van energieke elektries-gelaaide deeltjies, tot in die magnetosfeer, met die gevolg dat magnetosferiese elektriese stroomstelsels versterk word. 'n Toename in die ekwatoriale ringstrome lei spesifiek tot 'n afname in die horisontale komponent van die geomagnetiese veld. Geomagnetiese storms word dus gekenmerk deur 'n sterk afname in die horisontale komponent van die geomagnetiese veld, ‘n afname wat etlike ure tot dae kan duur. Die intensiteit van 'n storm word beskryf deur die storm-tyd versteurings indeks , 'n maatstaf van die afwyking van die tipiese stil dag magnetiese variasie langs die ewenaar. Ernstige storms kan lei tot die ontwrigting van hoë frekwensie (HF) kommunikasie as 'n gevolg van 'n erg versteurde ionosfeer. Soortgelyk kan die Globale Posisionering Stelsel (GPS) hoogs onbetroubaar word tydens magneties versteurde toestande, en posisiefoute so groot as 50 meter veroorsaak. Die impak van geomagnetiese aktiwiteit en ander sonkrag gedrewe prosesse op tegnologie is gesamentlik bekend as ruimteweer. Magneetveldmetinge vorm dus 'n belangrike deel van ruimteweervoorspelling en is noodsaaklik vir ruimtewetenskaplike navorsing as 'n middel om die sonwind-magnetosfeer interaksies beter te verstaan. Hierdie studie ondersoek die gebruik van SQUID (Engels: Superconducting Quantum Interference Device) magnetometers vir die monitering van die geomagnetiese veld vir ruimteweervoorspellingsdoeleindes. ’n Basiese teorie van supergeleiding word aangebied, waarvolgens die sleutelaspekte van SQUIDs bespreek word. Ruimteweer word ook voorgestel in terme van die verskillende prosesse op die son wat die aarde se magnetosfeer en dus die geomagnetiese veld versteur. Die analisemetode wat hier gebruik word, is om die Fourier-transform van data met die Wiener-Khintchine theorema te bereken. A sistematiese metode vir Fourier-analise word aangebied, wat die superiorireit van die Wiener-Khintchine teorema vir ruisvermindering demonstreer. Die geskiktheid van SQUID magnetometers vir ruimtewetenskaplike navorsing word gedemonstreer deur ’n vergelykende studie tussen SQUID- en vloedhek-datastelle vir magnetiese storms gedurende 2011. Sterk korrelasie is waargeneem tussen die frekwensie-inhoud van die SQUID- en vloedhekseine. Hierdie resultate ondersteun Suid-Afrika se SQUID-projek, wat tans as ’n samewerkingspoging tussen SANSA Space Science en die Departement Elektriese en Elektroniese Ingenieurswese aan die Universiteit van Stellenbosch bedryf word. Hierdie tesis lê ’n fondasie vir toekomstige navorsing oor gevorderde magnetometrie met SQUIDs.

Thesis (MEng)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: Superconducting QUantum Interference Devices (SQUIDs) are fairly recent types of magnetometers that use flux quantization combined with Josephson tunnelling to detect very faint (< 10¯15 T) magnetic fields. Recent scientific studies have shown that these highly sensitive magnetometers, located in an ultra-low-noise environment, are capable of observing Earth-ionosphere couplings, such as P waves emitted during earthquakes or magnetic storms in the upper atmosphere, S and T breathing modes of the Earth during quiet magnetic and seismic periods, signals in time correlating with sprites. Since SQUIDs are much more sensitive than conventional magnetometers, they are arguably the best tool for understanding space weather and natural hazards, whether they are produced from space or within the ionosphere by magnetic storms for instance, or natural disturbances, including magnetic disturbances produced by earthquakes or as a result of the dynamics of the earth's core. A study was conducted at SANSA Space Science in Hermanus, Western Cape, in 2012, to find the correlation between SQUID and Fluxgate data-sets, with the aim of validating the use of a SQUID as a reliable instrument for Space Weather observations. In that study, SQUID data obtained from the Low Noise Laboratory (LSBB) in France was compared to Fluxgate data-sets from the three closest magnetic observatories to LSBB, namely Chambon la For êt (France), Ebro (Spain) and Fürstenfeldbruck (Germany), all further than 500 km from LSBB. As a follow-up study, our aim is to correlate the SANSA Space Science SQUID data at Hermanus with Fluxgate magnetic data also recorded on-site (at Hermanus). There are notable di_erences between the previous study and the current study. In the previous study, the three-axis SQUID used comprised of three low-Tc devices operated in liquid helium (4.2 K) in an underground, low noise environment shielded from most human interferences. The SQUID magnetometer operated at Hermanus for the duration of this study is a high-Tc two-axis device (measuring the x and z components of the geomagnetic field). This SQUID magnetometer operates in liquid nitrogen (77 K), and is completely unshielded in the local geomagnetic field of about 26 uT. The environment is magnetically clean to observatory standards, but experiences more human interference than that at LSBB. The high-Tc SQUIDs also experience excessive 1/f noise at low frequencies which the low-Tc SQUIDs do not suffer from, but the big advantage of the current study is that the SQUIDs are located within 50 m from the observatory's fluxgate. We thus expect far better correlation between SQUID and fluxgate data than what was obtained in the previous study, which should improve the isolation of signals detected by the SQUID but not by the fluxgate. / AFRIKAANSE OPSOMMING: SQUIDs (supergeleidende kwantuminterferensietoestelle) is redelik onlangse tipes magnetometers wat vloedkwantisering saam met Josephson-tonneling gebruik om baie klein (< 10¯15 T) magnetiese velde waar te neem. Onlangse wetenskaplike studies het getoon dat hierdie hoogs sensitiewe magnetometers die vermoë het om Aarde-ionosfeerkoppeling waar te neem wanneer dit in 'n ultra-laeruisomgewing geplaas word. Sodanige koppeling sluit in: P-golwe wat deur aardbewings or magnetiese storms in die boonste atmosfeer veroorsaak word; S- en T-asemhalingsmodusse van die Aarde gedurende stil magnetiese en seismiese periodes; en seine in tyd wat korreleer met weerligeffekte in die boonste atmosfeer. Aangesien SQUIDs heelwat meer sensistief is as konvensionele magnetometers, is dit moontlik die beste gereedskap om ruimteweer en geassosieerde natuurlike gevare mee te analiseer; hetsy sulke toestande veroorsaak word vanaf die ruimte (deur die son) of binne die ionosfeer deur magnetiese storms of natuurlike steurings wat deur aardbewings of die dinamika van die Aardkern veroorsaak word. 'n Studie is in 2012 gedoen by SANSA Space Science in Hermanus in die Wes-Kaap om die korrelasie tussen SQUID- en vloedhekdatastelle te vind met die doel om SQUIDs as betroubare instrumente vir ruimteweerwaarneming te bevestig. In daardie studie is SQUID-data verkry vanaf die Laeruis Ondergrondse Laboratorium (LSBB) in Frankryk, en is dit vergelyk met vloedhekdatastelle vanaf die drie naaste magnetiese observatoriums aan LSBB, naamlik: Chambon la Forêt (Frankryk), Ebro (Spanje) en Fürstenfeldbruck (Duitsland). Al drie hierdie observatoriums is verder as 500 km vanaf LSBB. As 'n opvolgstudie is ons doelwit om SQUID- en vloedhekdata wat beide op die terrein van SANSA Space Science in Hermanus waargeneem word, te korreleer. Daar is merkbare verskille tussen hierdie en die vorige studies. In die vorige studie is 'n drie-as lae-Tc SQUID-magnetometer in vloeibare helium (4.2 K) in 'n laeruis ondergrondse laboratorium, afgeskerm teen menslike steurings, gebruik. Die SQUID-magnetometer wat vir die duur van die huidige studie by Hermanus gebruik is, is 'n hoë-Tc twee-as toestel (wat die x - en z -komponente van die geomagnetiese veld meet). Hierdie SQUID-magnetometer opereer in vloeibare stikstof teen 77 K, sonder enige afskerming in die geomagnetiese veld van ongeveer 26 uT. Die omgewing is magneties skoon volgens observatoriumstandaarde, maar ondervind meer menslik-veroorsaakde steurings as LSBB. Die hoë-Tc SQUIDs tel ook heelwat 1/f ruis op (wat lae-frekwensiemetings beïnvloed); iets wat nie 'n rol speel by die lae-Tc SQUIDs nie. Die groot voordeel van die huidige studie is dat die SQUIDs binne 50 meter vanaf die observatorium vloedhekke geleë is. Ons verwag dus heelwat beter korrelasie tussen SQUID- en vloedhekdata as wat met die vorige studie verkry is, wat dit makliker sal maak om die isolasie te verbeter van seine wat deur die SQUIDs waargeneem is, maar nie deur die vloedhekke nie.

This thesis presents a combined experimental and computational evaluation of the physical-organic properties of butadiyne-linked porphyrin oligomers. The principal result from the thesis is the synthesis and characterisation of the largest aromatic and antiaromatic systems to date, in the form of an oxidised [6]-porphyrin nanoring, with diameter 2.4 nm. This large electronically coherent system provides insight into the connection between aromatic ring currents and persistent currents in metal and semiconductor mesoscopic rings. Chapter 1 briefly reviews the concepts used in the remainder of the thesis, with a particular focus on aromaticity. In Chapter 2, the barrier to inter-porphyrin torsional rotation in a butadiyne-linked porphyrin dimer is determined computationally and experimentally to be 3 kJ mol^-1. The barrier height is closely related to the resonance delocalisation energy between the porphyrin subunits. In Chapter 3 we show that by oxidising a butadiyne-linked [6]-porphyrin nanoring to its 4+ and 6+ oxidation states, the nanoring becomes antiaromatic and aromatic respectively. In contrast, the neutral oxidation state exhibits only local aromaticity for the six porphyrin units. The 12+ cation can also be generated, and exhibits local antiaromaticity for each porphyrin unit. The characterisation of (anti)aromaticity employs NMR and computational techniques. In Chapter 4, the properties of cation radicals of linear and cyclic porphyrin oligomers are explored. Cations generated by spectroelectrochemistry are measured by optical spectroscopies, and chemically generated radical monocations are examined by cw/pulsed EPR spectroscopies. EPR and optical spectroscopies agree that the dimer monocation radical is fully delocalised, in Robin-Day Class III, whereas the monocations of longer oligomers are localised over 2-3 porphyrin units (Class II). In Chapter 5, photophysical and computational investigations into excited state aromaticity in porphyrin nanorings are presented. The computational results suggest the presence of aromaticity in the triplet excited states, but experiment fails to convincingly demonstrate the effect. Computational results in Chapter 6 show that a butadiyne linked [6]-porphyrin nanoring in which one butadiyne (C≡C-C≡C) is truncated to an alkyne (C≡C) exhibits a reversal of aromaticity and antiaromaticity in its oxidised states, compared to the all-butadiyne linked nanoring, consistent with Hückel's law.

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