The magnetosphere-ionosphere contains a number of current systems. These currents vary on a wide range of spatial and temporal scales and physically couple with each other. To study the complicated behaviors of these coupled current systems, the ground-based magnetometer has been a useful tool, but the recorded magnetometer data are always multi-scaled and intermittent due to the nature of these current systems. To distinguish these geomagnetic effects with multiple temporal and frequency scales, the wavelet analysis technique is especially suitable because of its special abilities of presenting information in both temporal and frequency domains. In this dissertation, the geomagnetic disturbances and the ring current variability during storm and quiet times are studied by using wavelet analysis and ground-based magnetic data from multiple stations. The first part of this dis- sertation investigates the strengths of applying the wavelet procedure to geomagnetic data for ring current study during storm and quiet periods. The second part of this dissertation characterizes the geomagnetic effects caused by symmetric and asymmetric components of ring currents during storm and quiet times by applying wavelet analysis to geomagnetic data from multiple stations. The third part of this dissertation studies the spatial variabil- ity of the symmetric ring current by applying the wavelet analysis technique to multiple components of magnetic data from multiple stations. The results show the unique strengths of the wavelet method allow us to quantitatively distinguish the geomagnetic effects on ring current variations from other M-I current systems. The unique strengths of wavelet method also allow us to separate the magnetic effects of the symmetric ring current from those caused by the asymmetric ring current. Quantitative information of the spatial variability of the ring currents is essential for understanding the dynamics of the ring currents, as well as the magnetic storm processes. The techniques developed in this dissertation have potential values as space weather monitoring tools for satellite controls, power grids, com- munication systems, oil pipelines, and other high-tech systems that are vulnerable to the negative impacts of disruptive geomagnetic events.

In this thesis we describe a coupled model of Earth's magnetosphere that consists of the Lyon-Fedder-Mobarry (LFM) global magnetohydrodynamics (MHD) simulation, the MIX ionosphere solver and the Rice Convection Model (RCM). We report some results of the coupled model using idealized inputs and model parameters. The algorithmic and physical components of the model are described, including the transfer of magnetic field information and plasma boundary conditions to the RCM and the return of ring current plasma properties to the LFM. Crucial aspects of the coupling include the restriction of RCM to regions where field-line averaged plasma-beta <=1, the use of a plasmasphere model, and the MIX ionosphere model. Compared to stand-alone MHD, the coupled model produces a substantial increase in ring current pressure and reduction of the magnetic field near the Earth. In the ionosphere, stronger region-1 and region-2 Birkeland currents are seen in the coupled model but with no significant change in the cross polar cap potential drop, while the region-2 currents shielded the low-latitude convection potential. In addition, oscillations in the magnetic field are produced at geosynchronous orbit with the coupled code. The diagnostics of entropy and mass content indicate that these oscillations are associated with low-entropy flow channels moving in from the tail and may be related to bursty bulk flows and bubbles seen in observations. As with most complex numerical models, there is the ongoing challenge of untangling numerical artifacts and physics, and we find that while there is still much room for improvement, the results presented here are encouraging. Finally, we introduce several new methods for magnetospheric visualization and analysis, including a fluid-spatial volume for RCM and a field-aligned analysis mesh for the LFM. The latter allows us to construct novel visualizations of flux tubes, drift surfaces, topological boundaries, and bursty-bulk flows.

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第22263号 / 理博第4577号 / 新制||理||1657(附属図書館) / 京都大学大学院理学研究科地球惑星科学専攻 / (主査)教授 田口 聡, 教授 秋友 和典, 准教授 藤 浩明 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20089号 / 工博第4256号 / 新制||工||1659(附属図書館) / 33205 / 京都大学大学院工学研究科電気工学専攻 / (主査)教授 大村 善治, 教授 松尾 哲司, 准教授 小嶋 浩嗣 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

<p>This thesis deals with the development and calibrations of sensors to measure energetic neutral atoms (ENAs) at Mars, Venus, and the Earth. ENAs are formed in charge exchange processes between energetic, singly--charged ions and a cold neutral gas. Since ENAs can travel in long straight trajectories, unaffected by electric or magnetic fields, they can be used to remotely image plasma interactions with neutral atmospheres. ENA instrument techniques have matured over the last decade and ENA images of the Earth's ring current for example, have successfully been analyzed to extract ion distributions and characterize plasma flows and currents in the inner magnetosphere.</p><p>Three different ENA sensors have been developed to image ENAs at Mars, Venus, and the Earth. Two of them, the nearly identical Neutral Particle imagers (NPIs) are on-board the Mars Express and Venus Express spacecraft as a part of the Analyzer of Space Plasmas and Energetic Atoms (ASPERA-3 and 4) instruments. The third is the Neutral Atom Detector Unit, NUADU, aboard the TC-2 spacecraft of the Double Star mission. The NPI design is based on a surface reflection technique to measure low energy (~0.3-60 keV) ENAs, while the NUADU instrument is based on a simple design with large geometrical factor and solid state detectors to measure high energy ENAs (~20-300 keV).</p><p>The calibration approach of both NPI sensors were to define the detailed response, including properties such as the angular response function and efficiency of one reference sensor direction then find the relative response of the other sensor directions. Because of the simple geometry of the NUADU instrument, the calibration strategy involved simulations to find the cutoff energy, geometrical factor and angular response. The NUADU sensor head was then calibrated to find the response to particles of different mass and energy. The NPI sensor for the Mars Express mission revealed a so-called priority effect in the sensor that lowers the angular resolution at high detector bias. During the calibration of the Venus Express NPI sensor tests were made which showed that the priority effect is a result of low amplitude (noise) pulses generated in the detector system. The conclusion is that the effect is caused by capacitive couplings between different anode sectors of the sensor. The thresholds on the preamplifiers were set higher on the Venus Express NPI, which removed the priority effect.</p><p>Two of the three ENA experiments, the Double Star NUADU instrument and the Mars Express NPI sensor, have successfully measured ENAs that are briefly described in the thesis. The first ENA measurements at Mars were performed with Mars Express. Initial results from the NPI include measurements of ENAs formed in the Martian magnetosheath and solar wind ENAs penetrating to the nightside of Mars. The first results from NUADU in Earth orbit show the expected ENA emissions from a storm time ring current. Also, together with the HENA instrument on the IMAGE spacecraft, NUADU have produced the first multi-point ENA image of the ring current.</p>

This thesis deals with the development and calibrations of sensors to measure energetic neutral atoms (ENAs) at Mars, Venus, and the Earth. ENAs are formed in charge exchange processes between energetic, singly--charged ions and a cold neutral gas. Since ENAs can travel in long straight trajectories, unaffected by electric or magnetic fields, they can be used to remotely image plasma interactions with neutral atmospheres. ENA instrument techniques have matured over the last decade and ENA images of the Earth's ring current for example, have successfully been analyzed to extract ion distributions and characterize plasma flows and currents in the inner magnetosphere. Three different ENA sensors have been developed to image ENAs at Mars, Venus, and the Earth. Two of them, the nearly identical Neutral Particle imagers (NPIs) are on-board the Mars Express and Venus Express spacecraft as a part of the Analyzer of Space Plasmas and Energetic Atoms (ASPERA-3 and 4) instruments. The third is the Neutral Atom Detector Unit, NUADU, aboard the TC-2 spacecraft of the Double Star mission. The NPI design is based on a surface reflection technique to measure low energy (~0.3-60 keV) ENAs, while the NUADU instrument is based on a simple design with large geometrical factor and solid state detectors to measure high energy ENAs (~20-300 keV). The calibration approach of both NPI sensors were to define the detailed response, including properties such as the angular response function and efficiency of one reference sensor direction then find the relative response of the other sensor directions. Because of the simple geometry of the NUADU instrument, the calibration strategy involved simulations to find the cutoff energy, geometrical factor and angular response. The NUADU sensor head was then calibrated to find the response to particles of different mass and energy. The NPI sensor for the Mars Express mission revealed a so-called priority effect in the sensor that lowers the angular resolution at high detector bias. During the calibration of the Venus Express NPI sensor tests were made which showed that the priority effect is a result of low amplitude (noise) pulses generated in the detector system. The conclusion is that the effect is caused by capacitive couplings between different anode sectors of the sensor. The thresholds on the preamplifiers were set higher on the Venus Express NPI, which removed the priority effect. Two of the three ENA experiments, the Double Star NUADU instrument and the Mars Express NPI sensor, have successfully measured ENAs that are briefly described in the thesis. The first ENA measurements at Mars were performed with Mars Express. Initial results from the NPI include measurements of ENAs formed in the Martian magnetosheath and solar wind ENAs penetrating to the nightside of Mars. The first results from NUADU in Earth orbit show the expected ENA emissions from a storm time ring current. Also, together with the HENA instrument on the IMAGE spacecraft, NUADU have produced the first multi-point ENA image of the ring current.

WINDMI is a low dimensional plasma physics-based model of the coupled magnetosphere-ionosphere system. The nonlinear system of ordinary differential equations describes the energy balance between the basic nightside components of the system using the solar wind driving voltage as input. Of the eight dynamical variables determined by the model, the region 1 field aligned current and ring current energy is compared to the westward auroral electrojet AL index and equatorial geomagnetic disturbance storm time Dst index. The WINDMI model is used to analyze the magnetosphere-ionosphere system during major geomagnetic storms and substorms which are community campaign events. Numerical experiments using the WINDMI model are also used to assess the question of how much interplanetary shock events contribute to the geoeffectiveness of solar wind drivers. For two major geomagnetic storm intervals, it is found that the magnetic field compressional jump is important to producing the changes in the AL index. Further, the WINDMI model is implemented to compute model AL and Dst predictions every ten minutes using real-time solar wind data from the ACE satellite as input. Real-Time WINDMI has been capturing substorm and storm activity, as characterized by the AL and Dst indices, reliably since February 2006 and is validated by comparison with ground-based measurements of the indices. Model results are compared for three different candidate input solar wind driving voltage formulas. Modeling of the Dst index is further developed to include the additional physical processes of tail current increases and sudden commencement. A new model, based on WINDMI, is developed using the dayside magnetopause and magnetosphere current systems to model the magnetopause boundary motion and the dayside region 1 field aligned current which is comparable to the auroral upper AU index. / text

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.

The cyclopentadienone-fused dihydropyrenes 46 and 47 were synthesized. The internal methyl resonances, the coupling constants, NICS calculations and X-ray results confirmed that the cyclopentadienone displays antiaromatic character resulting in bond localization in the annulene ring consistent with a 4n-pi fused system. The ring current of the dihydropyrene fragment is reduced by fusion of the antiaromatic system by about 80% of that caused by benzene. The syntheses of the methylfulvene fused dihydropyrene 56 and the phenylfulvene fused dihydropyrene 58 have been accomplished. The calculated and experimental NMR data and NICS calculations all demonstrated that the fulvenes had weak diatropic ring currents and caused bond localizations in the DHP rings, in which phenyl fulvene has a larger effect than that of methyl fulvene. A number of bis-dihydropyrene systems, bis-dihydropyrene ketone 117, bis-benzo[e]dihydropyrene ketone 119, benzo[e]dihydropyrene dihydropyrene ketone 122, bis-benzo[e]dihydropyrene methylene 124 and the benzo[e]dihydropyrene- dihydropyrene acetylene 130, have been synthesized, in which 117, 119 and 124 are homo-systems and 122 and 130 are hetero-systems. The multiple photoswitching properties study found that all of these systems except 130 showed multi-states during the photo opening and photo closing processes, which means that each end of the DHP units photo opens or closes separately rather than synchronously. In the homo switches 117, 119 and 124, the two DHP units act independently, but the relative differentiation is not very significant. On the other hand, the hetero-switch 122 showed fully differentiated photo opening process and almost a pure open-closed intermediate 122’ could be achieved. This is the first example which clearly showed four states in the UV closing process. The relative photo opening and closing rates compared to benzoDHP 36 have also been studied. It was found that while the carbonyl linker largely increased the relative photo opening rate (117, 119 and 122), the methylene linker only increased it slightly (124). The photo closing processes were always fast as usual. The studies of the thermal return reactions of these systems showed that while the carbonyl linker substantially slowed down the thermal return reactions of the DHP units (117, 119 and 122), the methylene linker speeded it up slightly (124). The mono-iron tricarbonyl benzo[e]dihydropyrene complex 152, the bis-iron tricarbonyl benzo[e]dihydropyrene complex 153 and the iron tetracarbonyl dihydropyrene complex 151 were synthesized. The structures of 152 and 153 were determined by X-ray crystallography. The coordinations of iron tricarbonyl moieties to the DHP rings caused a distortion of ca. 30 degree away from the central DHP plane. Coordination also increased bond alternation and reduced ring currents in the DHP rings. 1H-NMR and X-ray studies showed that 152 showed a weak paratropic ring current in the DHP ring. Iron coordination of the DHP completely stopped the photochromic properties of the dihydropyrenes.

The synthesis of benzo[e]dimethyldihydropyrene (BDHP) photoswitches with ter-27, quarter-36, and quinque-28 thiophene oligomers attached on the same side of the switch was achieved using Stille coupling reactions. BDHP photoswitches with bi-75, ter-76 and quinque-77 thiophene oligomers attached directly to the switch on one side, and via a carbonyl spacer on the opposite side of the switch were also synthesized. Dimethyldihydropyrene (DHP) photoswitches with a naphthoyl functional group in the 2 position were synthesized using a Friedel Crafts reaction, and ter-96, quinque-97 and septi-98 thiophene oligomers were attached on opposite sides of the switch using Stille coupling reactions. All compounds were characterized by NMR, IR UV-vis spectroscopy and mass spectrometry. The relative rates of the photo-opening reactions under excess light conditions and the UV closing reactions versus BDHP were measured. Improvements in the photo-opening properties of the oligothiophene functionalized switches compared to BDHP were observed. The most dramatic photo-opening improvement was found for the quinquethienyl substituted DHP switch 97 which photo-opened when irradiated with visible light over 100 times faster than BDHP. UV closing rates were virtually the same as that of BDHP. However the addition of oligothiophenes led to an increase in the thermal closing reaction rates. Compounds with the naphthoyl functional group in the 2 position of DHP were found to have dramatically increased thermal closing rates. The electrochemical properties of oligothiophene functionalized BDHP and naphthoyl functionalized DHP switches in the closed form were studied by cyclic voltammetry and spectroelectrochemistry. During the oxidation cycle, a closing reaction from the cyclophanediene (CPD) form to the DHP form of the switches occurred which prevented the study of the electrochemical properties of the switches in the open form. Conductivity testing was performed on the quinquethienyl substituted DHP switch 97 using a gold interdigitated micro electrode array. The conductivity of undoped 97 was greater in the closed DHP isomer than in the open CPD isomer. Irradiation with red or blue light allowed for repetitive switching between the more highly conducting closed form and the less conducting open form. When electrochemically doped, 97 showed improved conductivity over the undoped form but only the conductivity of the closed doped form could be measured due to electrochemically induced closing.