Refine
Year of publication
Document Type
- Doctoral Thesis (12)
- Article (6)
- Postprint (6)
- Habilitation Thesis (1)
- Other (1)
Keywords
- spectroscopy (26) (remove)
We theoretically discuss the interaction of neutral particles (atoms, molecules) with surfaces in the regime where it is mediated by the electromagnetic field. A thorough characterization of the field at sub-wavelength distances is worked out, including energy density spectra and coherence functions. The results are applied to typical situations in integrated atom optics, where ultracold atoms are coupled to a thermal surface, and to single molecule probes in near field optics, where sub-wavelength resolution can be achieved.
With the present theoretical study of the photochemical switching of E-methylfurylfulgide we contribute an important step towards the understanding of the photochemical processes in furylfulgide-related molecules. We have carried out large-scale, full-dimensional direct semiempirical configuration-interaction surface-hopping dynamics of the photoinduced ring-closure reaction. Simulated static and dynamical UV/Vis-spectra show good agreement with experimental data of the same molecule. By a careful investigation of our dynamical data, we were able to identify marked differences to the dynamics of the previously studied E-isopropylfurylfulgide. With our simulations we can not only reproduce the experimentally observed quantum yield differences qualitatively but we can also pinpoint two reasons for them: kinematics and pre-orientation. With our analysis, we thus offer straightforward molecular explanations for the high sensitivity of the photodynamics towards seemingly minor changes in molecular constitution. Beyond the realm of furylfulgides, these insights provide additional guidance to the rational design of photochemically switchable molecules.
In der vorliegenden Arbeit werden verschiedene Spektrometer für die Analyse von Gasen bzw. Gasgemischen vorgestellt und deren Design, Aufbau, Charakterisierung und Optimierung beschrieben. Das Resultat der Optimierung und Weiterentwicklungen ist ein spektral breitbandiges Cavity-Ring-Down-Spektrometer (CRD-Spektrometer). Ausgangspunkt der hier vorgestellten Arbeit ist ein Spektrometer auf Basis klassischer Absorptionsspektroskopie in einer Multireflexionszelle. Für dieses Spektrometer wurde als Strahlquelle ein Superkontinuumlaser verwendet. Der Vorteil dieses Spektrometers liegt in seiner Kompaktheit. Mit diesem Spektrometer wurden Absorptionsspektren von mehreren Reingasen und einem Gasgemisch über einen Wellenlängenbereich von 1500 nm – 1700 nm aufgenommen. Der qualitative Vergleich mit zu erwartenden Spektren, welche auf der HITRAN-Datenbank basieren, zeigte eine gute Übereinstimmung. Die quantitative Interpretierbarkeit der Daten war jedoch stark eingeschränkt aufgrund des hohen zufälligen und systematischen Fehlers der Messungen. Als Konsequenz aus der als nicht zufriedenstellend bewerteten quantitativen Interpretierbarkeit der Daten wurde eine alternative Messmethode gesucht, welche eine höhere Sensitivität und Genauigkeit ermöglicht. Die Wahl fiel auf die Cavity-Ring-Down-Spektroskopie, eine resonatorgestützte Variante der Absorptionsspektroskopie. Wesentliche Vorteile dieser Technik sind a) die Unabhängigkeit von Leistungsschwankungen der Strahlquelle, b) ein effektiver Absorptionsweg von bis zu mehreren Kilometern, welcher sich unmittelbar auf die Sensitivität der Messungen auswirkt, c) die Ermittlung absoluter Absorberkonzentrationen, ohne die Notwendigkeit einer Kalibrierung oder den Vergleich mit einer Referenzzelle und d) die Vernachlässigbarkeit von Absorptionen außerhalb des Resonators. Als notwendiger Zwischenschritt auf dem Weg zu einem breitbandigen CRD-Spektrometer wurde zunächst ein monochromatisches CRD-Spektrometer designt, aufgebaut und charakterisiert. Für die effektive Einkopplung von Strahlungsenergie in einen Resonator ist die Anpassung der Strahlparameter an die Mode des Resonators notwendig. Voraussetzung dieser Anpassung ist die Kenntnis der Strahlparameter, welche experimentell ermittelt wurden. Im Laufe des Aufbaus des Spektrometers ergab sich, dass trotz der Modenanpassung die Einkopplung der Strahlungsenergie in den Resonator gestört wurde. Daraufhin wurden systematisch mögliche Ursachen dieser Störung untersucht und das Spektrometer optimiert. Mit diesem optimierten Spektrometer wurden Spektren gemessen, welche sowohl qualitativ als auch quantitativ gut mit den zu erwartenden Spektren übereinstimmen. Als Nachweisgrenze dieses Spektrometers wurde ein Wert für den Absorptionskoeffizienten alpha von 10^-8 cm-1 bestimmt. Mit dem monochromatischen CRD-Spektrometer war es zudem möglich, isotopenspezifische Messungen durchzuführen. Für das breitbandige Spektrometer wurde als Strahlquelle eine ASE-Diode (amplified spontaneous emission) verwendet. Dabei handelt es sich um eine inkohärente Strahlquelle. Mittels Messungen nach dem Prinzip der Cavity-Enhanced-Absorptionsspektroskopie wurde die generelle Funktionalität des resonatorgestützten Spektrometers überprüft. Anschließend wurden die wellenlängenabhängigen Abklingsignale des leeren und des mit einem CO2-Luft-Gemisch gefüllten Resonators gemessen und ebenfalls mit den zu erwartenden Spektren verglichen. Qualitativ stimmen die experimentellen Spektren gut mit den zu erwartenden Spektren überein. Für die quantitative Interpretation der Daten wurde ein spezieller Algorithmus entwickelt, der die spektrale Auflösung des Systems berücksichtigt. Mit dem vorgestellten Spektrometer ist so die qualitative und quantitative Interpretation der Spektren möglich. Die Nachweisgrenze des breitbandigen Cavity-Ring-Down-Spektrometers wurde zu einem Wert von alpha = 8x10^-7 cm-1 bestimmt. Der systematischen und der zufällige Fehler der Messungen lagen bei Werten von ca. 1%. Bei diesem Spektrometer handelt es sich um einen Prototyp. Mittels Optimierung des Systems lassen sich sowohl der Wert der Nachweisgrenze als auch die Fehler der Messungen verbessern.
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.
Spectral fingerprinting
(2015)
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 Isábena 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.
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.
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.
In this combined theoretical and experimental study we report a full analysis of the resonant inelastic X-ray scattering (RIXS) spectra of H2O, D2O and HDO. We demonstrate that electronically-elastic RIXS has an inherent capability to map the potential energy surface and to perform vibrational analysis of the electronic ground state in multimode systems. We show that the control and selection of vibrational excitation can be performed by tuning the X-ray frequency across core-excited molecular bands and that this is clearly reflected in the RIXS spectra. Using high level ab initio electronic structure and quantum nuclear wave packet calculations together with high resolution RIXS measurements, we discuss in detail the mode coupling, mode localization and anharmonicity in the studied systems.
The problem of atmospheric emission from OH molecules is a long standing problem for near-infrared astronomy. PRAXIS is a unique spectrograph which is fed by fibres that remove the OH background and is optimised specifically to benefit from OH-Suppression. The OH suppression is achieved with fibre Bragg gratings, which were tested successfully on the GNOSIS instrument. PRAXIS uses the same fibre Bragg gratings as GNOSIS in its first implementation, and will exploit new, cheaper and more efficient, multicore fibre Bragg gratings in the second implementation. The OH lines are suppressed by a factor of similar to 1000, and the expected increase in the signal-to-noise in the interline regions compared to GNOSIS is a factor of similar to 9 with the GNOSIS gratings and a factor of similar to 17 with the new gratings. PRAXIS will enable the full exploitation of OH suppression for the first time, which was not achieved by GNOSIS (a retrofit to an existing instrument that was not OH-Suppression optimised) due to high thermal emission, low spectrograph transmission and detector noise. PRAXIS has extremely low thermal emission, through the cooling of all significantly emitting parts, including the fore-optics, the fibre Bragg gratings, a long length of fibre, and the fibre slit, and an optical design that minimises leaks of thermal emission from outside the spectrograph. PRAXIS has low detector noise through the use of a Hawaii-2RG detector, and a high throughput through a efficient VPH based spectrograph. PRAXIS will determine the absolute level of the interline continuum and enable observations of individual objects via an IFU. In this paper we give a status update and report on acceptance tests.
Radio-frequency fields in the GHz range are increasingly applied in biotechnology and medicine. In order to fully exploit both their potential and their risks detailed information about the dielectric properties of biological material is needed. For this purpose a measuring system is presented that allows the acquisition of complex dielectric spectra over 4 frequency decade up to 110 GHz. Routines for calibration and for data evaluation according to physicochemical interaction models have been developed. The frequency dependent permittivity and dielectric loss of some proteins and nucleic acids, the main classes of biomolecules, and of their sub-units have been determined. Dielectric spectra are presented for the amino acid alanine, the proteins lysozyme and haemoglobin, the nucleotides AMP and ATP, and for the plasmid pET-21, which has been produced by bacterial culture. Characterisation of a variety of biomolecules is envisaged, as is the application to studies on protein structure and function.