Studies of electronic structure by x-ray Raman and emission spectroscopy: applications to MgB2 superconductors and high pressure physics

X-ray Raman scattering and x-ray emission spectroscopies were used to study the electronic properties and phase transitions in several condensed matter systems. The experimental work, carried out at the European Synchrotron Radiation Facility, was complemented by theoretical calculations of the x-ray spectra and of the electronic structure. The electronic structure of MgB2 at the Fermi level is dominated by the boron σ and π bands. The high density of states provided by these bands is the key feature of the electronic structure contributing to the high critical temperature of superconductivity in MgB2. The electronic structure of MgB2 can be modified by atomic substitutions, which introduce extra electrons or holes into the bands. X ray Raman scattering was used to probe the interesting σ and π band hole states in pure and aluminum substituted MgB2. A method for determining the final state density of electron states from experimental x-ray Raman scattering spectra was examined and applied to the experimental data on both pure MgB2 and on Mg(0.83)Al(0.17)B2. The extracted final state density of electron states for the pure and aluminum substituted samples revealed clear substitution induced changes in the σ and π bands. The experimental work was supported by theoretical calculations of the electronic structure and x-ray Raman spectra. X-ray emission at the metal Kβ line was applied to the studies of pressure and temperature induced spin state transitions in transition metal oxides. The experimental studies were complemented by cluster multiplet calculations of the electronic structure and emission spectra. In LaCoO3 evidence for the appearance of an intermediate spin state was found and the presence of a pressure induced spin transition was confirmed. Pressure induced changes in the electronic structure of transition metal monoxides were studied experimentally and were analyzed using the cluster multiplet approach. The effects of hybridization, bandwidth and crystal field splitting in stabilizing the high pressure spin state were discussed. Emission spectroscopy at the Kβ line was also applied to FeCO3 and a pressure induced iron spin state transition was discovered.

Use of biomass fuels in the brick-making industries of Sudan: Implications for deforestation and greenhouse gas emission

The study focuses on the potential roles of the brick making industries in Sudan in deforestation and greenhouse gas emission due to the consumption of biofuels. The results were based on the observation of 25 brick making industries from three administrative regions in Sudan namely, Khartoum, Kassala and Gezira. The methodological approach followed the procedures outlined by the Intergovernmental Panel on Climate Change (IPCC). For predicting a serious deforestation scenario, it was also assumed that all of wood use for this particular purpose is from unsustainable sources. The study revealed that the total annual quantity of fuelwood consumed by the surveyed brick making industries (25) was 2,381 t dm. Accordingly, the observed total potential deforested wood was 10,624 m3, in which the total deforested round wood was 3,664 m3 and deforested branches was 6,961 m3. The study observed that a total of 2,990 t biomass fuels (fuelwood and dung cake) consumed annually by the surveyed brick making industries for brick burning. Consequently, estimated total annual emissions of greenhouse gases were 4,832 t CO2, 21 t CH4, 184 t CO, 0.15 t N20, 5 t NOX and 3.5 t NO while the total carbon released in the atmosphere was 1,318 t. Altogether, the total annual greenhouse gases emissions from biomass fuels burning was 5,046 t; of which 4,104 t from fuelwood and 943 t from dung cake burning. According to the results, due to the consumption of fuelwood in the brick making industries (3,450 units) of Sudan, the amount of wood lost from the total growing stock of wood in forests and trees in Sudan annually would be 1,466,000 m3 encompassing 505,000 m3 round wood and 961,000 m3 branches annually. By considering all categories of biofuels (fuelwood and dung cake), it was estimated that, the total emissions from all the brick making industries of Sudan would be 663,000 t CO2, 2,900 t CH4, 25,300 t CO, 20 t N2O, 720 t NOX and 470 t NO per annum, while the total carbon released in the atmosphere would be 181,000 t annually.

Informational efficiency of the European Union emission allowance market

This thesis studies the informational efficiency of the European Union emission allowance (EUA) market. In an efficient market, the market price is unpredictable and profits above average are impossible in the long run. The main research problem is does the EUA price follow a random walk. The method is an econometric analysis of the price series, which includes an autocorrelation coefficient test and a variance ratio test. The results reveal that the price series is autocorrelated and therefore a nonrandom walk. In order to find out the extent of predictability, the price series is modelled with an autoregressive model. The conclusion is that the EUA price is autocorrelated only to a small degree and that the predictability cannot be used to make extra profits. The EUA market is therefore considered informationally efficient, although the price series does not fulfill the requirements of a random walk. A market review supports the conclusion, but it is clear that the maturing of the market is still in process.

Two views on interstellar dust: near-infrared scattering and polarized thermal dust emission

Interstellar clouds are not featureless, but show quite complex internal structures of filaments and clumps when observed with high enough resolution. These structures have been generated by 1) turbulent motions driven mainly by supernovae, 2) magnetic fields working on the ions and, through neutral-ion collisions, on neutral gas as well, and 3) self-gravity pulling a dense clump together to form a new star. The study of the cloud structure gives us information on the relative importance of each of these mechanisms, and helps us to gain a better understanding of the details of the star formation process. Interstellar dust is often used as a tracer for the interstellar gas which forms the bulk of the interstellar matter. Some of the methods that are used to derive the column density are summarized in this thesis. A new method, which uses the scattered light to map the column density in large fields with high spatial resolution, is introduced. This thesis also takes a look at the grain alignment with respect to the magnetic fields. The aligned grains give rise to the polarization of starlight and dust emission, thus revealing the magnetic field. The alignment mechanisms have been debated for the last half century. The strongest candidate at present is the radiative torques mechanism. In the first four papers included in this thesis, the scattered light method of column density estimation is formulated, tested in simulations, and finally used to obtain a column density map from observations. They demonstrate that the scattered light method is a very useful and reliable tool in column density estimation, and is able to provide higher resolution than the near-infrared color excess method. These two methods are complementary. The derived column density maps are also used to gain information on the dust emissivity within the observed cloud. The two final papers present simulations of polarized thermal dust emission assuming that the alignment happens by the radiative torques mechanism. We show that the radiative torques can explain the observed decline of the polarization degree towards dense cores. Furthermore, the results indicate that the dense cores themselves might not contribute significantly to the polarized signal, and hence one needs to be careful when interpreting the observations and deriving the magnetic field.

Studies on Aerosol Particle Emission, Sampling and Authenticity

Emissions of coal combustion fly ash through real scale ElectroStatic Precipitators (ESP) were studied in different coal combustion and operation conditions. Sub-micron fly-ash aerosol emission from a power plant boiler and the ESP were determined and consequently the aerosol penetration, as based on electrical mobility measurements, thus giving thereby an indication for an estimate on the size and the maximum extent that the small particles can escape. The experimentals indicate a maximum penetration of 4% to 20 % of the small particles, as counted on number basis instead of the normally used mass basis, while simultaneously the ESP is operating at a nearly 100% collection efficiency on mass basis. Although the size range as such seems to appear independent of the coal, of the boiler or even of the device used for the emission control, the maximum penetration level on the number basis depends on the ESP operating parameters. The measured emissions were stable during stable boiler operation for a fired coal, and the emissions seemed each to be different indicating that the sub-micron size distribution of the fly-ash could be used as a specific characteristics for recognition, for instance for authenticity, provided with an indication of known stable operation. Consequently, the results on the emissions suggest an optimum particle size range for environmental monitoring in respect to the probability of finding traces from the samples. The current work embodies also an authentication system for aerosol samples for post-inspection from any macroscopic sample piece. The system can comprise newly introduced new devices, for mutually independent use, or, for use in a combination with each other, as arranged in order to promote the sampling operation length and/or the tag selection diversity. The tag for the samples can be based on naturally occurring measures and/or added measures of authenticity in a suitable combination. The method involves not only military related applications but those in civil industries as well. Alternatively to the samples, the system can be applied to ink for note printing or other monetary valued papers, but also in a filter manufacturing for marking fibrous filters.

Development of biogenic VOC emission inventories for the boreal forest

Luonnosta haihtuvat orgaaniset yhdisteet, joita pääsee ilmaan etenkin metsistä, voivat vaikuttaa paikalliseen ja alueelliseen ilmanlaatuun, koska ne reagoivat ilmakehässä. Niiden reaktiotuotteet voivat myös osallistua uusien hiukkasten muodostumiseen ja kasvuun, millä voi olla vaikutusta ilmakehän säteilytaseeseen ja tätä kautta myös ilmastoon. Hiukkaset absorboivat ja sirottavat auringon säteilyä ja maapallon lämpösäteilyä minkä lisäksi ne vaikuttavat pilvien säteilyominaisuuksiin, määrään ja elinikään. Koko maapallon mittakaavassa luonnosta tulevat hiilivetypäästöt ylittävät ihmistoiminnan aiheuttamat päästöt moninkertaisesti. Tämän vuoksi luonnon päästöjen arviointi on tärkeää kun halutaan kehittää tehokkaita ilmanlaatu- ja ilmastostrategioita. Tämä tutkimus käsittelee boreaalisen metsän hiilivetypäästöjä. Boreaalinen metsä eli pohjoinen havumetsä on suurin maanpäällinen ekosysteemi, ja se ulottuu lähes yhtenäisenä nauhana koko pohjoisen pallonpuoliskon ympäri. Sille on tyypillistä puulajien suhteellisen pieni kirjo sekä olosuhteiden ja kasvun voimakkaat vuodenaikaisvaihtelut. Työssä on tutkittu Suomen yleisimmän boreaalisen puun eli männyn hiilivetypäästöjen vuodenaikaisvaihtelua sekä päästöjen riippuvuutta lämpötilasta ja valosta. Saatuja tuloksia on käytetty yhdessä muiden boreaalisilla puilla tehtyjen päästömittaustulosten kanssa Suomen metsiä varten kehitetyssä päästömallissa. Malli perustuu lisäksi maankäyttötietoihin, suomen metsille kehitettyyn luokitukseen ja meteorologisiin tietoihin, joiden avulla se laskee metsien hiilivetypäästöt kasvukauden aikana. Suomen metsien päästöt koostuvat koko kasvukauden ajan suurelta osin alfa- ja beta-pineenistä sekä delta-kareenista. Kesällä ja syksyllä päästöissä on myös paljon sabineenia, jota tulee etenkin lehtipuista. Päästöt seuraavat lämpötilan keskimääräistä vaihtelua, ovat suurimmillaan maan eteläosissa ja laskevat tasaisesti pohjoiseen siirryttäessä. Metsän isopreenipäästö on suhteellisen pieni – Suomessa tärkein isopreeniä päästävä puu on vähäpäästöinen kuusi, koska runsaspäästöisten pajun ja haavan osuus metsän lehtimassasta on hyvin pieni. Tässä työssä on myös laskettu ensimmäinen arvio metsän seskviterpeenipäästöistä. Seskviterpeenipäästöt alkavat Juhannuksen jälkeen ja ovat kasvukauden aikana samaa suuruusluokkaa kuin isopreenipäästöt. Vuositasolla Suomen metsien hiilivetypäästöt ovat noin kaksinkertaiset ihmistoiminnasta aiheutuviin päästöihin verrattuna.

Studies of solar and stellar flares using multi-instrument data

Solar flares were first observed by plain eye in white light by William Carrington in England in 1859. Since then these eruptions in the solar corona have intrigued scientists. It is known that flares influence the space weather experienced by the planets in a multitude of ways, for example by causing aurora borealis. Understanding flares is at the epicentre of human survival in space, as astronauts cannot survive the highly energetic particles associated with large flares in high doses without contracting serious radiation disease symptoms, unless they shield themselves effectively during space missions. Flares may be at the epicentre of man s survival in the past as well: it has been suggested that giant flares might have played a role in exterminating many of the large species on Earth, including dinosaurs. Having said that prebiotic synthesis studies have shown lightning to be a decisive requirement for amino acid synthesis on the primordial Earth. Increased lightning activity could be attributed to space weather, and flares. This thesis studies flares in two ways: in the spectral and the spatial domain. We have extracted solar spectra using three different instruments, namely GOES (Geostationary Operational Environmental Satellite), RHESSI (Reuven Ramaty High Energy Solar Spectroscopic Imager) and XSM (X-ray Solar Monitor) for the same flares. The GOES spectra are low resolution obtained with a gas proportional counter, the RHESSI spectra are higher resolution obtained with Germanium detectors and the XSM spectra are very high resolution observed with a silicon detector. It turns out that the detector technology and response influence the spectra we see substantially, and are important to understanding what conclusions to draw from the data. With imaging data, there was not such a luxury of choice available. We used RHESSI imaging data to observe the spatial size of solar flares. In the present work the focus was primarily on current solar flares. However, we did make use of our improved understanding of solar flares to observe young suns in NGC 2547. The same techniques used with solar monitors were applied with XMM-Newton, a stellar X-ray monitor, and coupled with ground based Halpha observations these techniques yielded estimates for flare parameters in young suns. The material in this thesis is therefore structured from technology to application, covering the full processing path from raw data and detector responses to concrete physical parameter results, such as the first measurement of the length of plasma flare loops in young suns.

Characterization of non-imaging semiconductor X-ray solar monitors

The first observations of solar X-rays date back to late 1940 s. In order to observe solar X-rays the instruments have to be lifted above the Earth s atmosphere, since all high energy radiation from the space is almost totally attenuated by it. This is a good thing for all living creatures, but bad for X-ray astronomers. Detectors observing X-ray emission from space must be placed on-board satellites, which makes this particular discipline of astronomy technologically and operationally demanding, as well as very expensive. In this thesis, I have focused on detectors dedicated to observing solar X-rays in the energy range 1-20 keV. The purpose of these detectors was to measure solar X-rays simultaneously with another X-ray spectrometer measuring fluorescence X-ray emission from the Moon surface. The X-ray fluorescence emission is induced by the primary solar X-rays. If the elemental abundances on the Moon were to be determined with fluorescence analysis methods, the shape and intensity of the simultaneous solar X-ray spectrum must be known. The aim of this thesis is to describe the characterization and operation of our X-ray instruments on-board two Moon missions, SMART-1 and Chandrayaan-1. Also the independent solar science performance of these two almost similar X-ray spectrometers is described. These detectors have the following two features in common. Firstly, the primary detection element is made of a single crystal silicon diode. Secondly, the field of view is circular and very large. The data obtained from these detectors are spectra with a 16 second time resolution. Before launching an instrument into space, its performance must be characterized by ground calibrations. The basic operation of these detectors and their ground calibrations are described in detail. Two C-flares are analyzed as examples for introducing the spectral fitting process. The first flare analysis shows the fit of a single spectrum of the C1-flare obtained during the peak phase. The other analysis example shows how to derive the time evolution of fluxes, emission measures (EM) and temperatures through the whole single C4 flare with the time resolution of 16 s. The preparatory data analysis procedures are also introduced in detail. These are required in spectral fittings of the data. A new solar monitor design equipped with a concentrator optics and a moderate size of field of view is also introduced.

K -shell diagram and hypersatellite spectra of 4d transition elements

The K-shell diagram (K alpha(1,2) and K beta(1,3)) and hypersatellite (HS) (K-h alpha(1,2)) spectra of Y, Zr, Mo, and Pd have been measured with high energy-resolution using photoexcitation by 90 keV synchrotron radiation. Comparison of the measured and ab initio calculated HS spectra demonstrates the importance of quantum electrodynamical (QED) effects for the HS spectra. Phenomenological fits of the measured spectra by Voigt functions yield accurate values for the shift of the HS from the diagram lines, the splitting of the HS lines, and their intensity ratio. Good agreement with theory was found for all quantities except for the intensity ratio, which is dominated by the intermediacy of the coupling of the angular momenta. The observed deviations imply that our current understanding of the variation of the coupling scheme from LS to jj across the periodic table may require some revision.

Elliptic flow of thermal photons in heavy-ion collisions at Relativistic Heavy Ion Collider and Large Hadron Collider

We calculate the thermal photon transverse momentum spectra and elliptic flow in $\sqrt{s_{NN}} = 200$ GeV Au+Au collisions at RHIC and in $\sqrt{s_{NN}} = 2.76$ TeV Pb+Pb collisions at the LHC, using an ideal-hydrodynamical framework which is constrained by the measured hadron spectra at RHIC and LHC. The sensitivity of the results to the QCD-matter equation of state and to the photon emission rates is studied, and the photon $v_2$ is discussed in the light of the photonic $p_T$ spectrum measured by the PHENIX Collaboration. In particular, we make a prediction for the thermal photon $p_T$ spectra and elliptic flow for the current LHC Pb+Pb collisions.