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Silicate melts are major components of the Earth’s interior and as such they make an essential contribution in igneous processes, in the dynamics of the solid Earth and the chemical development of the entire Earth. Macroscopic physical and chemical properties such as density, compressibility, viscosity, degree of polymerization etc. are determined by the atomic structure of the melt. Depending on the pressure, but also on the temperature and the chemical composition, silicate melts show different structural properties. These properties are best described by the local coordination environment, i.e. symmetry and number of neighbors (coordination number) of an atom, as well as the distance between the central atom and its neighbors (inter-atomic distance). With increasing pressure and temperature, i.e. with increasing depth in the Earth, the density of the melt increases, which can lead to changes in coordination number and distances. If the coordination number remains the same, the distance usually decreases. If the coordination number increases, the distance can increase. These general trends can, however, vary greatly, which can be attributed in particular to the chemical composition.
Due to the fact that natural melts of the deep earth are not accessible to direct investigations, in order to understand their properties under the relevant conditions, extensive experimental and theoretical investigations have been carried out so far. This has often been studied using the example of amorphous samples of the end-members SiO2 and GeO2 , with the latter serving as a structural and chemical analog model to SiO2. Commonly, the experiments were carried out at high pressure and at room temperature. Natural melts are chemically much more complex than the simple end-member SiO2 and GeO2, so that observations made on them may lead to incorrect compression models. Furthermore, the investigations on glasses at room temperature can show potentially strong deviations from the properties of melts under natural thermodynamic conditions.
The aim of this thesis was to explain the influence of the composition and the temperature on the structural properties of the melts at high pressures. To understand this, we studied complex alumino-germanate and alumino-silicate glasses. More precisely, we studied synthetic glasses that have a composition like the mineral albite and like a mixture of albite-diopside at the eutectic point. The albite glass is structurally similar to a simplified granitic melt, while the albite-diopside glass simulates a simplified basaltic melt. To study the local coordination environment of the elements, we used X-ray absorption spectroscopy in combination with a diamond anvil cell. Because the diamonds have a high absorbance for X-rays with energies below 10 keV, the direct investigation of the geologically relevant elements such as Si, Al, Ca, Mg etc. with this spectroscopic probe technique in combination with a diamond anvil cell is not possible. Therefore the glasses were doped with Ge and Sr. These elements serve partially or fully as substitutes for important major elements. In this sense, Ge serves as an a substitute for Si and other network formers, while Sr replaces network modifiers such as Ca, Na, Mg etc.,
as well as other cations with a large ionic radius.
In the first step we studied the Ge K-edge in Ge-Albit-glass, NaAlGe3O8, at room temperature up to 131 GPa. This glass has a higher chemical complexity than SiO2 and GeO2, but it is still fully polymerized. The differences in the compression mechanism between this glass and the simple oxides can clearly be attributed to higher chemical complexity. The albite and albite-diopside compositions partially doped with Ge and Sr were probed at room temperature for Ge up to 164 GPa and for Sr up to 42 GPa. While the albite glass is nominally fully polymerized like NaAlGe3O8, the albite-diopside glass is partially depolymerized. The results show that structural changes take place in all three glasses in the first 25 to a maximum of 30 GPa, with both Ge and Sr reaching the maximum coordination number 6 and ∼9, respectively. At higher pressures, only isostructural shrinkage of the coordination polyhedra takes place in the glasses. The most important finding of the high pressure studies on the alumino-silicate and alumino-germanate glasses is that in these complex glasses the polyhedra show a much higher compressibility than what can be observed in the end-members. This is shown in particular by the strong shortening of the Ge-O distances in the amorphous NaAlGe3O8 and albite-diopside glass at pressures above 30 GPa.
In addition to the effects of the composition on the compaction process, we investigated the influence of temperature on the structural changes. To do this, we probed the albite-diopside glass, as it is chemically most similar to the melts in the lower mantle. We studied the Ge K edge of the sample with a resistively heated and a laser-heated diamond anvil cell, for a pressure range of up to 48 GPa and a temperature range of up to 5000 K. High temperatures at which the sample is liquid and that are relevant for the Earth mantle, have a significant impact on the structural transformation, with a shift of approx. 30% to significantly lower pressures, compared to the glasses at room temperature and below 1000 K.
The results of this thesis represent an important contribution to the understanding of the properties of melts at conditions of the lower mantle. In the context of the discussion about the existence and origin of ultra-dense silicate melts at the core-mantle boundary, these investigations show that the higher density compared to the surrounding material cannot be explained by only structural features, but by a distinct chemical composition. The results also suggest that only very low solubilities of noble gases are to be expected for melts in the lower mantle, so that the structural properties clearly influence the overall budget and transport of noble gases in the Earth’s mantle.
The optical properties of chromophores, especially organic dyes and optically active inorganic molecules, are determined by their chemical structures, surrounding media, and excited state behaviors. The classical optical go-to techniques for spectroscopic investigations are absorption and luminescence spectroscopy. While both techniques are powerful and easy to apply spectroscopic methods, the limited time resolution of luminescence spectroscopy and its reliance on luminescent properties can make its application, in certain cases, complex, or even impossible. This can be the case when the investigated molecules do not luminesce anymore due to quenching effects, or when they were never luminescent in the first place. In those cases, transient absorption spectroscopy is an excellent and much more sophisticated technique to investigate such systems. This pump-probe laser-spectroscopic method is excellent for mechanistic investigations of luminescence quenching phenomena and photoreactions. This is due to its extremely high time resolution in the femto- and picosecond ranges, where many intermediate or transient species of a reaction can be identified and their kinetic evolution can be observed. Furthermore, it does not rely on the samples being luminescent, due to the active sample probing after excitation. In this work it is shown, that with transient absorption spectroscopy it was possible to identify the luminescence quenching mechanisms and thus luminescence quantum yield losses of the organic dye classes O4-DBD, S4-DBD, and pyridylanthracenes. Hence, the population of their triplet states could be identified as the competitive mechanism to their luminescence. While the good luminophores O4-DBD showed minor losses, the S4-DBD dye luminescence was almost entirely quenched by this process. However, for pyridylanthracenes, this phenomenon is present in both the protonated and unprotonated forms and moderately effects the luminescence quantum yield. Also, the majority of the quenching losses in the protonated forms are caused by additional non-radiative processes introduced by the protonation of the pyridyl rings. Furthermore, transient absorption spectroscopy can be applied to investigate the quenching mechanisms of uranyl(VI) luminescence by chloride and bromide. The reduction of the halides by excited uranyl(VI) leads to the formation of dihalide radicals X^(·−2). This excited state redox process is thus identified as the quenching mechanism for both halides, and this process, being diffusion-limited, can be suppressed by cryogenically freezing the samples or by observing these interactions in media with a lower dielectric constant, such as ACN and acetone.
Angular momentum is a particularly sensitive probe into stellar evolution because it changes significantly over the main sequence life of a star. In this thesis, I focus on young main sequence stars of which some feature a rapid evolution in their rotation rates. This transition from fast to slow rotation is inadequately explored observationally and this work aims to provide insights into the properties and time scales but also investigates stellar rotation in young open clusters in general.
I focus on the two open clusters NGC 2516 and NGC 3532 which are ~150 Myr (zero-age main sequence age) and ~300 Myr old, respectively. From 42 d-long time series photometry obtained at the Cerro Tololo Inter-American Observatory, I determine stellar rotation periods in both clusters. With accompanying low resolution spectroscopy, I measure radial velocities and chromospheric emission for NGC 3532, the former to establish a clean membership and the latter to probe the rotation-activity connection.
The rotation period distribution derived for NGC 2516 is identical to that of four other coeval open clusters, including the Pleiades, which shows the universality of stellar rotation at the zero-age main sequence. Among the similarities (with the Pleiades) the "extended slow rotator sequence" is a new, universal, yet sparse, feature in the colour-period diagrams of open clusters. From a membership study, I find NGC 3532 to be one of the richest nearby open clusters with 660 confirmed radial velocity members and to be slightly sub-solar in metallicity. The stellar rotation periods for NGC 3532 are the first published for a 300 Myr-old open cluster, a key age to understand the transition from fast to slow rotation. The fast rotators at this age have significantly evolved beyond what is observed in NGC 2516 which allows to estimate the spin-down timescale and to explore the issues that angular momentum models have in describing this transition. The transitional sequence is also clearly identified in a colour-activity diagram of stars in NGC 3532. The synergies of the chromospheric activity and the rotation periods allow to understand the colour-activity-rotation connection for NGC 3532 in unprecedented detail and to estimate additional rotation periods for members of NGC 3532, including stars on the "extended slow rotator sequence".
In conclusion, this thesis probes the transition from fast to slow rotation but has also more general implications for the angular momentum evolution of young open clusters.
The majority of baryons in the Universe is believed to reside in the intergalactic medium (IGM). This makes the IGM an important component in understanding cosmological structure formation. It is expected to trace the same dark matter distribution as galaxies, forming structures like filaments and clusters. However, whereas galaxies can be observed to be arranged along these large-scale structures, the spatial distribution of the diffuse IGM is not as easily unveiled. Absorption line studies of quasar (QSO) spectra can help with mapping the IGM, as well as the boundary layer between IGM and galaxies: the circumgalactic medium (CGM). By studying gas in the Local Group, as well as in the IGM, this study aims to get a better understanding of how the gas is linked to the large-scale structure of the local Universe and the galaxies residing in that structure.
Chapter 1 gives an introduction to the CGM and IGM, while the methods used in this study are explained in Chapter 2. Chapter 3 starts on a relatively small cosmological scale, namely that of our Local Group, which includes i.a. the Milky Way (MW) and the M31. Within the CGM of the MW, there exist denser clouds, some of which are infalling while others are moving away from the Galactic disc. To study these clouds, 29 QSO spectra obtained with the Cosmic Origins Spectrograph (COS) aboard the Hubble Space Telescope (HST) were analysed. Abundances of Si II, Si III, Si IV, C II, and C IV were measured for 69 HVCs belonging to two samples: one in the direction of the LG’s barycentre and the other in the anti-barycentre direction. Their velocities range from -100 ≥ vLSR ≥ -400 km/s for the barycentre sample and between +100 ≤ vLSR ≤ +300 km/s for the anti-barycentre sample. By using Cloudy models, these data could then be used to derive gas volume densities for the HVCs. Because of the relationship between density and pressure of the ambient medium, which is in turn determined by the Galactic radiation field, the distances of the HVCs could be estimated. From this, a subsample of absorbers located in the direction of M31 was found to exist outside of the MW’s virial radius, their low densities (log nH ≤ -3.54) making it likely for them to be part of the gas in between the MW and M31. No such low-density absorbers were found in the anti-barycentre sample. Our results thus hint at gas following the dark matter potential, which would be deeper between the MW and M31 as they are by far the most massive members of the LG.
From this bridge of gas in the LG, this study zooms out to the large-scale structure of the local Universe (z ~ 0) in Chapter 4. Galaxy data from the V8k catalogue and QSO spectra from COS were used to study the relation between the galaxies tracing large-scale filaments and the gas existing outside of those galaxies. This study used the filaments defined in Courtois et al. (2013). A total of 587 Lyman α (Lyα) absorbers were found in the 302 QSO spectra in the velocity range 1070 - 6700 km/s. After selecting sightlines passing through or close to these filaments, model spectra were made for 91 sightlines and 215 (227) Lyα absorbers (components) were measured in this sample. The velocity gradient along each filament was calculated and 74 absorbers were found within 1000 km/s of the nearest filament segment.
In order to find whether the absorbers are more tied to galaxies or to the large-scale structure, equivalent widths of the Lyα absorbers were plotted against both galaxy and filament impact parameters. While stronger absorbers do tend to be closer to either galaxies or filaments, there is a large scatter in this relation. Despite this large scatter, this study found that the absorbers do not follow a random distribution either. They cluster less strongly around filaments than galaxies, but stronger than random distributions, as confirmed by a Kolmogorov-Smirnov test.
Furthermore, the column density distribution function found in this study has a slope of -β = 1.63±0.12 for the total sample and -β =1.47±0.24 for the absorbers within 1000 km/s of a filament. The shallower slope for the latter subsample could indicate an excess of denser absorbers within the filament, but they are consistent within errors. These values are in agreement with values found in e.g. Lehner et al. (2007); Danforth et al. (2016).
The picture that emerges from this study regarding the relation between the IGM and the large-scale structure in the local Universe fits with what is found in other studies: while at least part of the gas traces the same filamentary structure as galaxies, the relation is complex. This study has shown that by taking a large sample of sightlines and comparing the data gathered from those with galaxy data, it is possible to study the gaseous large-scale structure. This approach can be used in the future together with simulations to get a better understanding of structure formation and evolution in the Universe.