@phdthesis{Anders2017,
  author    = {Anders, Friedrich},
  title     = {Disentangling the chemodynamical history of the Milky Way disc with asteroseismology and spectroscopy},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-396681},
  school      = {Universit{\"a}t Potsdam},
  pages     = {121},
  year      = {2017},
  abstract  = {Galaxies are among the most complex systems that can currently be modelled with a computer. A realistic simulation must take into account cosmology and gravitation as well as effects of plasma, nuclear, and particle physics that occur on very different time, length, and energy scales. The Milky Way is the ideal test bench for such simulations, because we can observe millions of its individual stars whose kinematics and chemical composition are records of the evolution of our Galaxy. Thanks to the advent of multi-object spectroscopic surveys, we can systematically study stellar populations in a much larger volume of the Milky Way. While the wealth of new data will certainly revolutionise our picture of the formation and evolution of our Galaxy and galaxies in general, the big-data era of Galactic astronomy also confronts us with new observational, theoretical, and computational challenges. This thesis aims at finding new observational constraints to test Milky-Way models, primarily based on infra-red spectroscopy from the Apache Point Observatory Galactic Evolution Experiment (APOGEE) and asteroseismic data from the CoRoT mission. We compare our findings with chemical-evolution models and more sophisticated chemodynamical simulations. In particular we use the new powerful technique of combining asteroseismic and spectroscopic observations that allows us to test the time dimension of such models for the first time. With CoRoT and APOGEE (CoRoGEE) we can infer much more precise ages for distant field red-giant stars, opening up a new window for Galactic archaeology. Another important aspect of this work is the forward-simulation approach that we pursued when interpreting these complex datasets and comparing them to chemodynamical models. The first part of the thesis contains the first chemodynamical study conducted with the APOGEE survey. Our sample comprises more than 20,000 red-giant stars located within 6 kpc from the Sun, and thus greatly enlarges the Galactic volume covered with high-resolution spectroscopic observations. Because APOGEE is much less affected by interstellar dust extinction, the sample covers the disc regions very close to the Galactic plane that are typically avoided by optical surveys. This allows us to investigate the chemo-kinematic properties of the Milky Way's thin disc outside the solar vicinity. We measure, for the first time with high-resolution data, the radial metallicity gradient of the disc as a function of distance from the Galactic plane, demonstrating that the gradient flattens and even changes its sign for mid-plane distances greater than 1 kpc. Furthermore, we detect a gap between the high- and low-[\$\alpha\$/Fe] sequences in the chemical-abundance diagram (associated with the thin and thick disc) that unlike in previous surveys can hardly be explained by selection effects. Using 6D kinematic information, we also present chemical-abundance diagrams cleaned from stars on kinematically hot orbits. The data allow us to confirm without doubt that the scale length of the (chemically-defined) thick disc is significantly shorter than that of the thin disc. In the second part, we present our results of the first combination of asteroseismic and spectroscopic data in the context of Galactic Archaeology. We analyse APOGEE follow-up observations of 606 solar-like oscillating red giants in two CoRoT fields close to the Galactic plane. These stars cover a large radial range of the Galactic disc (4.5 kpc \$\lesssim R_{\rm Gal}\lesssim15\$ kpc) and a large age baseline (0.5 Gyr \$\lesssim \tau\lesssim\$ 13 Gyr), allowing us to study the age- and radius-dependence of the [\$\alpha\$/Fe] vs. [Fe/H] distributions. We find that the age distribution of the high-[\$\alpha\$/Fe] sequence appears to be broader than expected from a monolithically-formed old thick disc that stopped to form stars 10 Gyr ago. In particular, we discover a significant population of apparently young, [\$\alpha\$/Fe]-rich stars in the CoRoGEE data whose existence cannot be explained by standard chemical-evolution models. These peculiar stars are much more abundant in the inner CoRoT field LRc01 than in the outer-disc field LRc01, suggesting that at least part of this population has a chemical-evolution rather than a stellar-evolution origin, possibly due to a peculiar chemical-enrichment history of the inner disc. We also find that strong radial migration is needed to explain the abundance of super-metal-rich stars in the outer disc. Finally, we use the CoRoGEE sample to study the time evolution of the radial metallicity gradient in the thin disc, an observable that has been the subject of observational and theoretical debate for more than 20 years. By dividing the CoRoGEE dataset into six age bins, performing a careful statistical analysis of the radial [Fe/H], [O/H], and [Mg/Fe] distributions, and accounting for the biases introduced by the observation strategy, we obtain reliable gradient measurements. The slope of the radial [Fe/H] gradient of the young red-giant population (\$-0.058\pm0.008\$ [stat.] \$\pm0.003\$ [syst.] dex/kpc) is consistent with recent Cepheid data. For the age range of \$1-4\$ Gyr, the gradient steepens slightly (\$-0.066\pm0.007\pm0.002\$ dex/kpc), before flattening again to reach a value of \$\sim-0.03\$ dex/kpc for stars with ages between 6 and 10 Gyr. This age dependence of the [Fe/H] gradient can be explained by a nearly constant negative [Fe/H] gradient of \$\sim-0.07\$ dex/kpc in the interstellar medium over the past 10 Gyr, together with stellar heating and migration. Radial migration also offers a new explanation for the puzzling observation that intermediate-age open clusters in the solar vicinity (unlike field stars) tend to have higher metallicities than their younger counterparts. We suggest that non-migrating clusters are more likely to be kinematically disrupted, which creates a bias towards high-metallicity migrators from the inner disc and may even steepen the intermediate-age cluster abundance gradient.},
  language  = {en}
}
@phdthesis{Brosinsky2015,
  author    = {Brosinsky, Arlena},
  title     = {Spectral fingerprinting},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-83369},
  school      = {Universit{\"a}t Potsdam},
  pages     = {VI, 117},
  year      = {2015},
  abstract  = {Current research on runoff and erosion processes, as well as an increasing demand for sustainable watershed management emphasize the need for an improved understanding of sediment dynamics. This involves the accurate assessment of erosion rates and sediment transfer, yield and origin. A variety of methods exist to capture these processes at the catchment scale. Among these, sediment fingerprinting, a technique to trace back the origin of sediment, has attracted increasing attention by the scientific community in recent years. It is a two-step procedure, based on the fundamental assumptions that potential sources of sediment can be reliably discriminated based on a set of characteristic 'fingerprint' properties, and that a comparison of source and sediment fingerprints allows to quantify the relative contribution of each source. This thesis aims at further assessing the potential of spectroscopy to assist and improve the sediment fingerprinting technique. Specifically, this work focuses on (1) whether potential sediment sources can be reliably identified based on spectral features ('fingerprints'), whether (2) these spectral fingerprints permit the quantification of relative source contribution, and whether (3) in situ derived source information is sufficient for this purpose. Furthermore, sediment fingerprinting using spectral information is applied in a study catchment to (4) identify major sources and observe how relative source contributions change between and within individual flood events. And finally, (5) spectral fingerprinting results are compared and combined with simultaneous sediment flux measurements to study sediment origin, transport and storage behaviour. For the sediment fingerprinting approach, soil samples were collected from potential sediment sources within the Is{\´a}bena catchment, a meso-scale basin in the central Spanish Pyrenees. Undisturbed samples of the upper soil layer were measured in situ using an ASD spectroradiometer and subsequently sampled for measurements in the laboratory. Suspended sediment was sampled automatically by means of ISCO samplers at the catchment as well as at the five major subcatchment outlets during flood events, and stored fine sediment from the channel bed was collected from 14 cross-sections along the main river. Artificial mixtures of known contributions were produced from source soil samples. Then, all source, sediment and mixture samples were dried and spectrally measured in the laboratory. Subsequently, colour coefficients and physically based features with relation to organic carbon, iron oxide, clay content and carbonate, were calculated from all in situ and laboratory spectra. Spectral parameters passing a number of prerequisite tests were submitted to principal component analyses to study natural clustering of samples, discriminant function analyses to observe source differentiation accuracy, and a mixing model for source contribution assessment. In addition, annual as well as flood event based suspended sediment fluxes from the catchment and its subcatchments were calculated from rainfall, water discharge and suspended sediment concentration measurements using rating curves and Quantile Regression Forests. Results of sediment flux monitoring were interpreted individually with respect to storage behaviour, compared to fingerprinting source ascriptions and combined with fingerprinting to assess their joint explanatory potential. In response to the key questions of this work, (1) three source types (land use) and five spatial sources (subcatchments) could be reliably discriminated based on spectral fingerprints. The artificial mixture experiment revealed that while (2) laboratory parameters permitted source contribution assessment, (3) the use of in situ derived information was insufficient. Apparently, high discrimination accuracy does not necessarily imply good quantification results. When applied to suspended sediment samples of the catchment outlet, the spectral fingerprinting approach was able to (4) quantify the major sediment sources: badlands and the Villacarli subcatchment, respectively, were identified as main contributors, which is consistent with field observations and previous studies. Thereby, source contribution was found to vary both, within and between individual flood events. Also sediment flux was found to vary considerably, annually as well as seasonally and on flood event base. Storage was confirmed to play an important role in the sediment dynamics of the studied catchment, whereas floods with lower total sediment yield tend to deposit and floods with higher yield rather remove material from the channel bed. Finally, a comparison of flux measurements with fingerprinting results highlighted the fact that (5) immediate transport from sources to the catchment outlet cannot be assumed. A combination of the two methods revealed different aspects of sediment dynamics that none of the techniques could have uncovered individually. In summary, spectral properties provide a fast, non-destructive, and cost-efficient means to discriminate and quantify sediment sources, whereas, unfortunately, straight-forward in situ collected source information is insufficient for the approach. Mixture modelling using artificial mixtures permits valuable insights into the capabilities and limitations of the method and similar experiments are strongly recommended to be performed in the future. Furthermore, a combination of techniques such as e.g. (spectral) sediment fingerprinting and sediment flux monitoring can provide comprehensive understanding of sediment dynamics.},
  language  = {en}
}
@misc{CoutoCruzErtanetal.2017,
  author    = {Couto, Rafael C. and Cruz, Vinicius V. and Ertan, Emelie and Eckert, Sebastian and Fondell, Mattis and Dantz, Marcus and Kennedy, Brian and Schmitt, Thorsten and Pietzsch, Annette and Guimar{\~a}es, Freddy F. and {\AA}gren, Hans and Gel'mukhanov, Faris and Odelius, Michael and Kimberg, Victor and F{\"o}hlisch, Alexander},
  title     = {Selective gating to vibrational modes through resonant X-ray scattering},
  series = {Postprints der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe},
  journal   = {Postprints der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe},
  number    = {1124},
  issn      = {1866-8372},
  doi       = {10.25932/publishup-43692},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-436926},
  pages     = {9},
  year      = {2017},
  abstract  = {The dynamics of fragmentation and vibration of molecular systems with a large number of coupled degrees of freedom are key aspects for understanding chemical reactivity and properties. Here we present a resonant inelastic X-ray scattering (RIXS) study to show how it is possible to break down such a complex multidimensional problem into elementary components. Local multimode nuclear wave packets created by X-ray excitation to different core-excited potential energy surfaces (PESs) will act as spatial gates to selectively probe the particular ground-state vibrational modes and, hence, the PES along these modes. We demonstrate this principle by combining ultra-high resolution RIXS measurements for gas-phase water with state-of-the-art simulations.},
  language  = {en}
}
@phdthesis{Fritzewski2021,
  author    = {Fritzewski, Dario Jasper},
  title     = {From fast to slow rotation in the open clusters NGC 2516 and NGC 3532},
  doi       = {10.25932/publishup-53135},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-531356},
  school      = {Universit{\"a}t Potsdam},
  pages     = {viii, 137},
  year      = {2021},
  abstract  = {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.},
  language  = {en}
}
@phdthesis{Haubitz2021,
  author    = {Haubitz, Toni},
  title     = {Transient absorption spectroscopy},
  doi       = {10.25932/publishup-53509},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-535092},
  school      = {Universit{\"a}t Potsdam},
  pages     = {xiii, 176},
  year      = {2021},
  abstract  = {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.},
  language  = {en}
}
@phdthesis{Henkel2004,
  author    = {Henkel, Carsten},
  title     = {Coherence theory of atomic de Broglie waves and electromagnetic near fields},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-0001272},
  school      = {Universit{\"a}t Potsdam},
  year      = {2004},
  abstract  = {Die Arbeit untersucht theoretisch die Wechselwirkung neutraler Teilchen (Atome, Molek{\"u}le) mit Oberfl{\"a}chen, soweit sie durch das elektromagnetische Feld vermittelt wird. Spektrale Energiedichten und Koh{\"a}renzfunktionen werden hergeleitet und liefern eine umfassende Charakterisierung des Felds auf der sub-Wellenl{\"a}ngen-Skala. Die Ergebnisse finden auf zwei Teilgebieten Anwendung: in der integrierten Atomoptik, wo ultrakalte Atome an thermische Oberfl{\"a}chen koppeln, und in der Nahfeldoptik, wo eine Aufl{\"o}sung unterhalb der Beugungsbegrenzung mit einzelnen Molek{\"u}len als Sonden und Detektoren erzielt werden kann.},
  language  = {en}
}
@phdthesis{Herenz2014,
  author    = {Herenz, Peter},
  title     = {A study of the absorption characteristics of gaseous galaxy halos in the local Universe},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-70513},
  school      = {Universit{\"a}t Potsdam},
  year      = {2014},
  abstract  = {Today, it is well known that galaxies like the Milky Way consist not only of stars but also of gas and dust. The galactic halo, a sphere of gas that surrounds the stellar disk of a galaxy, is especially interesting. It provides a wealth of information about in and outflowing gaseous material towards and away from galaxies and their hierarchical evolution. For the Milky Way, the so-called high-velocity clouds (HVCs), fast moving neutral gas complexes in the halo that can be traced by absorption-line measurements, are believed to play a crucial role in the overall matter cycle in our Galaxy. Over the last decades, the properties of these halo structures and their connection to the local circumgalactic and intergalactic medium (CGM and IGM, respectively) have been investigated in great detail by many different groups. So far it remains unclear, however, to what extent the results of these studies can be transferred to other galaxies in the local Universe. In this thesis, we study the absorption properties of Galactic HVCs and compare the HVC absorption characteristics with those of intervening QSO absorption-line systems at low redshift. The goal of this project is to improve our understanding of the spatial extent and physical conditions of gaseous galaxy halos in the local Universe. In the first part of the thesis we use HST /STIS ultraviolet spectra of more than 40 extragalactic background sources to statistically analyze the absorption properties of the HVCs in the Galactic halo. We determine fundamental absorption line parameters including covering fractions of different weakly/intermediately/highly ionized metals with a particular focus on SiII and MgII. Due to the similarity in the ionization properties of SiII and MgII, we are able to estimate the contribution of HVC-like halo structures to the cross section of intervening strong MgII absorbers at z = 0. Our study implies that only the most massive HVCs would be regarded as strong MgII absorbers, if the Milky Way halo would be seen as a QSO absorption line system from an exterior vantage point. Combining the observed absorption-cross section of Galactic HVCs with the well-known number density of intervening strong MgII absorbers at z = 0, we conclude that the contribution of infalling gas clouds (i.e., HVC analogs) in the halos of Milky Way-type galaxies to the cross section of strong MgII absorbers is 34\%. This result indicates that only about one third of the strong MgII absorption can be associated with HVC analogs around other galaxies, while the majority of the strong MgII systems possibly is related to galaxy outflows and winds. The second part of this thesis focuses on the properties of intervening metal absorbers at low redshift. The analysis of the frequency and physical conditions of intervening metal systems in QSO spectra and their relation to nearby galaxies offers new insights into the typical conditions of gaseous galaxy halos. One major aspect in our study was to regard intervening metal systems as possible HVC analogs. We perform a detailed analysis of absorption line properties and line statistics for 57 metal absorbers along 78 QSO sightlines using newly-obtained ultraviolet spectra obtained with HST /COS. We find clear evidence for bimodal distribution in the HI column density in the absorbers, a trend that we interpret as sign for two different classes of absorption systems (with HVC analogs at the high-column density end). With the help of the strong transitions of SiII λ1260, SiIII λ1206, and CIII λ977 we have set up Cloudy photoionization models to estimate the local ionization conditions, gas densities, and metallicities. We find that the intervening absorption systems studied by us have, on average, similar physical conditions as Galactic HVC absorbers, providing evidence that many of them represent HVC analogs in the vicinity of other galaxies. We therefore determine typical halo sizes for SiII, SiIII, and CIII for L = 0.01L∗ and L = 0.05L∗ galaxies. Based on the covering fractions of the different ions in the Galactic halo, we find that, for example, the typical halo size for SiIII is ∼ 160 kpc for L = 0.05L∗ galaxies. We test the plausibility of this result by searching for known galaxies close to the QSO sightlines and at similar redshifts as the absorbers. We find that more than 34\% of the measured SiIII absorbers have galaxies associated with them, with the majority of the absorbers indeed being at impact parameters ρ ≤160 kpc.},
  language  = {en}
}
@phdthesis{Krstulovic2021,
  author    = {Krstulovic, Marija},
  title     = {Local structure of network formers and network modifiers in silicate melts at high pressure and temperature conditions},
  doi       = {10.25932/publishup-51641},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-516415},
  school      = {Universit{\"a}t Potsdam},
  pages     = {137},
  year      = {2021},
  abstract  = {Silikatische Schmelzen sind wichtiger Bestandteil des Erdinneren und als solche leisten sie in magmatischen Prozessen einen wesentlichen Beitrag in der Dynamik der festen Erde und der chemischen Entwicklung des gesamten Erdk{\"o}pers. Makroskopische physikalische und chemische Eigenschaften wie Dichte, Kompressibilit{\"a}t, Viskosit{\"a}t, Polymerisationsgrad etc. sind durch die atomare Struktur der Schmelzen bestimmt. In Abh{\"a}ngigkeit vom Druck, aber auch von der Temperatur und der chemischen Zusammensetzung zeigen silikatische Schmelzen unterschiedliche strukturelle Eigenschaften. Diese Eigenschaften sind am besten durch die lokale Koordinationsumgebung, d.h. Symmetrie und Anzahl der Nachbarn (Koordinationszahl) eines Atoms, sowie dem Abstand zwischen Zentralatom und Nachbarn (atomarer Abstand) beschrieben. Mit steigendem Druck und Temperatur, das heißt mit der zunehmenden Tiefe in der Erde, nimmt die Dichte der Schmelzen zu, welches zur Ver{\"a}nderung von Koordinationszahl und Abst{\"a}nden f{\"u}hren kann. Bei gleichbleibender Koordinationszahl nimmt der Abstand in der Regel zu. Kommt es zu Erh{\"o}hung der Koordinationszahl kann der Abstand zunehmen. Diese allgemeinen Trends k{\"o}nnen allerdings stark variieren, welches insbesondere auf die chemische Zusammensetzung zur{\"u}ckzuf{\"u}hren ist. Dadurch, dass nat{\"u}rliche Schmelzen der tiefen Erde f{\"u}r direkte Untersuchungen nicht zug{\"a}nglich sind, um ihre Eigenschaften unter den relevanten Bedingungen zu verstehen, wurden umfangreiche experimentelle und theoretische Untersuchungen bisher durchgef{\"u}hrt. Dies wurde h{\"a}ufig am Beispiel von amorphen Proben der Endglieder SiO2, und GeO2 studiert, wobei letzteres als strukturelles und chemisches Analogmodell zu SiO2 dient. Meistens wurden die Experimente bei hohem Druck und bei Raumtemperatur durchgef{\"u}hrt. Nat{\"u}rliche Schmelzen sind chemisch deutlich komplexer als die einfachen Endglieder SiO2 und GeO2, so dass die Beobachtungen an diesen m{\"o}glicherweise zu falschen Verdichtungsmodellen f{\"u}hren k{\"o}nnen. Weiterhin k{\"o}nnen die Untersuchungen an Gl{\"a}sern bei Raumtemperatur potentiell starke Abweichungen zu Eigenschaften von Schmelzen bei nat{\"u}rlichen thermodynamischen Bedingungen aufweisen. Das Ziel dieser Dissertation war es zu erl{\"a}utern, welchen Einfluss die Zusammensetzung und die Temperatur auf die strukturelle Eigenschaften der Schmelzen unter hohen Dr{\"u}cken haben. Um das zu verstehen, haben wir komplexe alumino-germanatische und alumino-silikatische Gl{\"a}ser studiert. Genauer gesagt, wir haben synthetische Gl{\"a}ser studiert, die eine Zusammensetzung wie das Mineral Albit und wie eine Mischung von Albit-Diopsid im eutektischen Punkt haben. Das Albitglas {\"a}hnelt strukturell einer vereinfachten granitischen Schmelze, w{\"a}hrend das Albit-Diopsid-Glas eine vereinfachte basaltische Schmelze simuliert. Um die lokale Koordinationsumgebung der Elemente zu studieren, haben wir die R{\"o}ntgenabsorptionsspektroskopie in Kombination mit einer Diamantstempelzelle benutzt. Dadurch, dass die Diamanten eine hohe Absorption f{\"u}r R{\"o}ntgenstrahlung mit Energien unterhalb von 10 keV aufweisen, ist die unmittelbare Untersuchung der geologisch sehr relevanten Elemente wie Si, Al, Ca, Mg etc. mit dieser Spektroskopie in Kombination mit einer Diamantstempelzelle nicht m{\"o}glich. Deswegen wurden die Gl{\"a}ser mit Ge und Sr dotiert. Diese Elemente dienen teilweise oder vollst{\"a}ndig als Ersatzelemente f{\"u}r wichtige Hauptelemente. In diesem Sinne, dient Ge als Ersatzelement f{\"u}r Si und andere Netzwerkbildner, w{\"a}hrend Sr Netzwerkwandler wie Z.B. Ca, Na, Mg etc., sowie andere Kationen mit großem Ionenradius ersetzt. Im ersten Schritt haben wir die Ge K-Kante im Ge-Albit-Glass, NaAlGe3O8, bei Raumtemperatur bis 131 GPa untersucht. Dieses Glas hat eine h{\"o}here chemische Komplexit{\"a}t als SiO2 und GeO2, aber es ist immer noch vollst{\"a}ndig polymerisiert. Die Unterschiede im Verdichtungsmechanismus zwischen diesem Glas und den einfachen Oxiden k{\"o}nnen so eindeutig auf h{\"o}here chemische Komplexit{\"a}t zur{\"u}ckgef{\"u}hrt werden. Die partiell mit Ge und Sr dotierten Albit und Albit-Diopsid-Zusammensetzungen wurden bei Raumtemperatur f{\"u}r Ge bis 164 GPa und f{\"u}r Sr bis 42 GPa untersucht. W{\"a}hrend das Albitglass wie NaAlGe3O8 nominelll vollst{\"a}ndig polymerisiert ist, ist das Albit-Diopsid Glas teilweise depolymerisiert. Die Ergebnisse zeigen, dass in allen drei Gl{\"a}sern strukturelle An̈derungen in den ersten 25 bis maximal 30 GPa stattfinden, wobei beide Ge und Sr die maximale Koordinationszahl 6 bzw. ∼9 erreichen. Bei h{\"o}heren Dr{\"u}cken findet in den Gl{\"a}sern nur eine isostrukturelle Schrumpfung der Koordinationspolyeder statt. Der wichtigste Befund der Hochdruckstudien an den alumino-silikatischen und alumino-germanatischen Gl{\"a}sern ist, dass in diesen komplexen Gl{\"a}sern die Polyeder eine viel h{\"o}here Kompressibilit{\"a}t aufweisen als bei den Endgliedern zu beobachten. Das zeigt sich insbesondere durch die starke Verk{\"u}rzung der Ge-O Abst{\"a}nde in dem amorphen NaAlGe3O8 und Albit-Diopsid-Glas bei Dr{\"u}cken {\"u}ber 30 GPa. Zus{\"a}tzlich zu den Effekten der Zusammensetzung auf den Verdichtungsprozess, haben wir den Einfluss der Temperatur auf die strukturelle {\"A}nderungen untersucht. Dazu haben wir das Albit-Diopsid-Glas untersucht, da es den Schmelzen im unteren Mantel chemisch am {\"a}hnlichsten ist. Wir haben die Ge K-Kante der Probe mit einer resistiv-geheizten und einer Laser-geheizter Diamantstempelzelle untersucht, f{\"u}r einen Druckbereich bis zu 48 GPa, sowie einen Temperaturbereich bis 5000 K. Hohe Temperaturen, bei denen die Probe fl{\"u}ssig ist und die f{\"u}r den Erdmantel relevant sind, haben einen bedeutenden Einfluss auf die strukturelle Transformation. Diese wird um ca. 30\% zu deutlich niedrigeren Dr{\"u}cken verschoben, im Vergleich zu den Gl{\"a}sern bei Raumtemperatur und unterhalb von 1000 K. Die Ergebnisse dieser Dissertation stellen einen wichtigen Beitrag fur das Verst{\"a}ndnis der Eigenschaften von Schmelzen unter Bedingungen des unteren Mantels dar. Im Kontext der Diskussion {\"u}ber die Existenz und den Ursprung von silikatischen Schmelzen mit ultrahoher Dichte, welche an der Grenze zwischen Mantel und Erdkern aufgrund seismologischer Daten vermutet werden, zeigen diese Untersuchugen, dass die im Vergleich zur Umgebung h{\"o}here Dichte nicht durch strukturelle Besonderheiten, sondern durch eine besondere chemische Zusammensetzung erkl{\"a}rt werden m{\"u}ssen. Außerdem legen die Ergebnisse nahe, dass f{\"u}r Schmelzen im unteren Erdmantel nur sehr geringe L{\"o}slichkeiten von Edelgasen zu erwarten sind, so dass die strukturellen Eigenschaften deutlich den Gesamthaushalt und Transport der Edelgase im Erdmantel beeinflussen.},
  language  = {en}
}
@misc{KubinGuoKrolletal.2018,
  author    = {Kubin, Markus and Guo, Meiyuan and Kroll, Thomas and L{\"o}chel, Heike and K{\"a}llman, Erik and Baker, Michael L. and Mitzner, Rolf and Gul, Sheraz and Kern, Jan and F{\"o}hlisch, Alexander and Erko, Alexei and Bergmann, Uwe and Yachandra, Vittal and Yano, Junko and Lundberg, Marcus and Wernet, Philippe},
  title     = {Probing the oxidation state of transition metal complexes},
  series = {Postprints der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe},
  journal   = {Postprints der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe},
  number    = {656},
  issn      = {1866-8372},
  doi       = {10.25932/publishup-42505},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-425057},
  pages     = {17},
  year      = {2018},
  abstract  = {Transition metals in inorganic systems and metalloproteins can occur in different oxidation states, which makes them ideal redox-active catalysts. To gain a mechanistic understanding of the catalytic reactions, knowledge of the oxidation state of the active metals, ideally in operando, is therefore critical. L-edge X-ray absorption spectroscopy (XAS) is a powerful technique that is frequently used to infer the oxidation state via a distinct blue shift of L-edge absorption energies with increasing oxidation state. A unified description accounting for quantum-chemical notions whereupon oxidation does not occur locally on the metal but on the whole molecule and the basic understanding that L-edge XAS probes the electronic structure locally at the metal has been missing to date. Here we quantify how charge and spin densities change at the metal and throughout the molecule for both redox and core-excitation processes. We explain the origin of the L-edge XAS shift between the high-spin complexes Mn-II(acac)(2) and Mn-III(acac)(3) as representative model systems and use ab initio theory to uncouple effects of oxidation-state changes from geometric effects. The shift reflects an increased electron affinity of Mn-III in the core-excited states compared to the ground state due to a contraction of the Mn 3d shell upon core-excitation with accompanied changes in the classical Coulomb interactions. This new picture quantifies how the metal-centered core hole probes changes in formal oxidation state and encloses and substantiates earlier explanations. The approach is broadly applicable to mechanistic studies of redox-catalytic reactions in molecular systems where charge and spin localization/delocalization determine reaction pathways.},
  language  = {en}
}
@phdthesis{Menski2019,
  author    = {Menski, Antonia Isabell},
  title     = {Europium als strukturelle Sonde zur Analyse neuartiger Materialien},
  doi       = {10.25932/publishup-42714},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-427141},
  school      = {Universit{\"a}t Potsdam},
  pages     = {181},
  year      = {2019},
  abstract  = {Im Rahmen dieser Arbeit wird anhand von neuartigen Materialien das Potential der Europium-Lumineszenz f{\"u}r die strukturelle Analyse dargestellt. Bei diesen Materialien handelt es sich zum einen um Nanopartikel mit Matrizes aus mehreren Metall-Mischoxiden und Dotierungen durch die Sonde Europium und zum anderen um Metallorganische Netzwerke (MOFs), die mit Neodym , Samarium- und Europium-Ionen beladen sind. Die Synthese der aus der Kombination von Metalloxiden enthaltenen Nanopartikel ist unter milden Bedingungen mithilfe von speziell daf{\"u}r hergestellten Reagenzien erfolgt und hat zu sehr kleinen, amorphen Nanopartikeln gef{\"u}hrt. Durch eine nachfolgende Temperaturbehandlung hat sich die Kristallinit{\"a}t erh{\"o}ht. Damit verbunden haben sich auch die Kristallstruktur sowie die Position des Dotanden Europium ver{\"a}ndert. W{\"a}hrend die etablierte Methode der R{\"o}ntgendiffraktometrie einen Blick auf das Kristallgitter als Gesamtes erm{\"o}glicht, so trifft die Lumineszenz des Europiums durch die Sichtbarkeit einzelner Stark-Aufspaltungen Aussagen {\"u}ber dessen lokale Symmetrien. Die Symmetrie wird durch Sauerstofffehlstellen ver{\"a}ndert, welche die Sauerstoffleitf{\"a}higkeit der Nanopartikel beeinflussen. Diese ist f{\"u}r die Anwendung als Katalysatoren in industriellen Prozessen und ebenso als Sensoren und Therapeutika in biologischen Systemen von Bedeutung. Zur ersten katalytischen Charakterisierung werden die Proben mittels Temperatur-programmierter Reduktion untersucht. Des Weiteren werden die Mischoxid-Nanopartikel auch hinsichtlich ihrer Verwendbarkeit als Matrix in Aufkonversionsprozessen untersucht. Die Metallorganischen Netzwerke eignen sich aufgrund ihrer mikropor{\"o}sen Struktur f{\"u}r Anwendungen in der Speicherung gleichermaßen von Nutzgasen wie auch von Schadstoffen. Ebenfalls ist eine biologische Anwendung denkbar, die insbesondere den Bereich der drug delivery-Reagenzien betrifft. Erfolgt in die mikropor{\"o}sen Strukturen der Metallorganischen Netzwerke die Einlagerung von Lanthanoid-Ionen, so k{\"o}nnen diese bei der entsprechenden Kombination als Weißlicht-Emittierer fungieren. Dabei ist neben den Verh{\"a}ltnissen zwischen den Lanthanoid-Ionen auch die genaue Position innerhalb des Netzwerks sowie die Distanz zu anderen Ionen von Interesse. Zur Untersuchung dieser Fragestellungen wird die Umgebungssensitivit{\"a}t der Europium-Lumineszenz ausgenutzt. Die auf diese Weise festgestellte Formiat-Bildung h{\"a}ngt von zahlreichen Parametern ab. Insgesamt stellt sich die im Rahmen dieser Arbeit verwendete Methodik des Einsatzes von Europium als strukturelle Sonde in h{\"o}chstem Maße vielseitig dar und zeigt seine gr{\"o}ßte St{\"a}rke in der Kombination mit weiteren Methoden der Strukturanalytik. Die auf diese Weise genauestens charakterisierten neuartigen Materialien k{\"o}nnen nun gezielt und anwendungsfokussiert weiterentwickelt werden.},
  language  = {de}
}