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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
11

Femtosekunden Photolyse von Diiodmethan in überkritischen Fluiden: Konkurrenz zwischen Photodissoziation und Photoisomerisierung / Femtosecond Photolysis of Diiodomethane in Supercritical Fluids: Competition between Photodissociation and Photoisomerisation

Grimm, Christian 05 November 2003 (has links)
No description available.
12

The effect of neutron excess and nuclear deformation on dipole strength functions below the neutron separation energy - nuclear resonance fluorescence experiments on 124,128,132,134 Xe at ELBE and HI gamma S

Massarczyk, Ralph 28 October 2014 (has links) (PDF)
Within this thesis, nuclear resonance fluorescence experiments were analyzed which have been performed at the gamma ELBE facility of the Helmholtz-Zentrum Dresden-Rossendorf and the HI gamma S facility of the Triangle Universities Nuclear Laboratory. The dipole strength up to the neutron separation energy, its distribution as well as its split into electric and magnetic strength were determined. The influence of crucial nuclear parameters, like deformation and neutron excess, on the data was investigated. For the first time a whole set of enriched gaseous targets was measured in the energy region close to the neutron separation threshold. At ELBE the scattering of photons on four different isotopes 124, 128, 132, 134 Xe was investigated by irradiating containers with enriched target material with a broad bremsstrahlung distribution. The endpoint energies were chosen to be 12MeV. This ensures excitations up to the neutron separation threshold. The two isotopes 128, 134 Xe were measured in an additional campaign at HI gamma S facility. The region below the threshold was explored in detail in these experiments. A second, more model-independent determination of the cross section was possible. The work shows, how the measured spectra taken with high-purity germanium detectors, have to be corrected for several, partly overlapping effects in order to determine the complete excitation strength. The calculation of different backgrounds, detector response functions and the influence of inelastic scattering constitute the main part of the presented work. With the help of GEANT4 simulations the amount of not-nuclear scattered photons was estimated. GEANT4 was also used to test the influence of the extended targets on the detection efficiency and response. The code gamma DEX, which calculates deexcitation schemes based on statistical assumptions, was updated and finally used for the unfolding of the spectrum. The measured data is compared to different strength function models and a theoretical prediction based on a QRPA calculation. The summed strength is also set into comparison to other experimental data sets and a global trend for low-lying strength was found. This shows, that the nuclear deformation which has a large influence on the dipole strength above the threshold is only of minor impact for the strength at lower energies. Instead of this, the neutron excess seems to be the dominating factor for the strength in the investigated energy region. This work was supported by the German Research Foundation (DFG), Project No. SCHW883/1-1.
13

Organization of chemical reactions by phase separation

Bauermann, Jonathan 02 November 2022 (has links)
All living things are driven by chemical reactions. Reactions provide energy and transform matter. Thus, maintaining the system out of equilibrium. However, these chemical reactions have to be organized in space. One way for this spatial organization is via the process of phase separation. Motivated by the recent discovery of liquid-like droplets in cells, this thesis studies the organization of chemical reactions in phase-separated systems, with and without broken detailed balance. After introducing the underlying thermodynamic principles, we generalize mass-action kinetics to systems with homogeneous compartments formed by phase separation. Here, we discuss the constraints resulting from phase equilibrium on chemical reactions. We study the relaxation kinetics towards thermodynamic equilibrium and investigate non-equilibrium states that arise when detailed balance is broken in the rates of reactions such that phase and chemical equilibria contradict each other. We then turn to spatially continuous systems with spatial gradients within formed compartments. We derive thermodynamic consistent dynamical equations for reactions and diffusion processes in such systems. Again, we study the relaxation kinetics towards equilibrium and discuss non-equilibrium states. We investigate the dynamics of droplets in the presence of reactions with broken detailed balance. Furthermore, we introduce active droplet systems maintained away from equilibrium via coupling to reservoirs at their boundaries and organizing reactions solely within droplets. Here, detailed balance is only broken at the boundaries. Nevertheless, stationary chemically active droplets exist in open systems, and droplets can divide. To quantitatively study chemically active droplet systems in multi-component mixtures, we introduce an effective description. Therefore, we couple linearized reaction-diffusion equations via a moving interface within a sharp interface limit. At the interface, the boundary conditions are set by a local phase equilibrium and the continuity of fluxes. Equipped with these tools, we introduce and study protocell models of chemically active droplets. We explicitly model these protocells’ nutrient and waste dynamics, leading to simple models of their metabolism. Next, we study the energetics of these droplets and identify processes responsible for growth or shrinkage and maintaining the system out of equilibrium. Furthermore, we discuss the energy balance leading to the heating and cooling of droplets. Finally, we show why chemically active droplets do not spontaneously divide in two-dimensional systems with bulk-driven reactions. Here, droplets can elongate but do not pinch off. To have a minimal two-dimensional model with droplet division, we introduce additional reactions. When these reactions are localized at the interface and dependent on its mean curvature, droplets robustly divide in 2D. In summary, this thesis contributes to the theoretical understanding of how the existence of droplets changes the kinetics of reactions and, vice versa, how chemical reactions can alter droplet dynamics.:1 Introduction 1.1 Thermodynamics of phase separation 1.1.1 Phase equilibrium in the thermodynamic limit 1.1.2 Relaxation dynamics towards equilibrium 1.1.3 Local stability of homogeneous phases 1.2 Thermodynamics of chemical reactions in homogenous mixtures 1.2.1 Conserved densities and reaction extents 1.2.2 Equilibrium of chemical reactions 1.2.3 Mass-action kinetics towards equilibrium 1.3 Simultaneous equilibrium of chemical reactions and phase separation 1.4 Chemical reactions maintained away from equilibrium 1.5 Structure of this thesis 2 Chemical reactions in compartmentalized systems 2.1 Mass-action kinetics for compartments built by phase separation 2.1.1 Dynamical equations for densities and phase volumes 2.1.2 Relaxation kinetics in a simple example 2.2 Driven chemical reactions in compartmentalized systems 2.2.1 Non-equilibrium steady states at phase equilibrium 2.2.2 The tie line selecting manifold 2.3 Discussion 3 Dynamics of concentration fields in phase-separating systems with chemical reactions 3.1 Reaction-diffusion equations for phase-separating systems 3.2 Relaxation towards thermodynamic equilibrium in spatial systems 3.2.1 Relaxation kinetics and fast diffusion 3.2.2 Relaxation kinetics with spatial gradients 3.3 Driven chemical reactions in phase-separating systems 3.3.1 Driven chemical reaction and fast diffusion 3.3.2 Non-equilibrium steady states and spatial gradients 3.3.3 Droplets growth and ripening with driven chemical reactions 3.4 Boundary-driven chemically active droplets 3.4.1 Droplets in open systems 3.4.2 Non-equilibrium steady droplets and shape instabilities 3.5 Discussion 4 Chemically active droplets in the sharp interface limit 4.1 Droplet dynamics via reaction-diffusion equations coupled by a moving interface 4.2 Stationary interface positions in spherical symmetry 4.2.1 Interface conditions in closed systems 4.2.2 Interface conditions in open systems 4.3 Shape instabilities of spherical droplets 4.4 Discussion 5 Models of protocells and their metabolism as chemically active droplets 5.1 Breaking detailed balance in protocell models 5.1.1 Boundary-driven protocell models 5.1.2 Bulk-driven protocell models 5.2 Protocell dynamics 5.2.1 Steady states droplets 5.2.2 Shape stability of spherical symmetric droplets 5.3 Energetics of protocells 5.3.1 Mass conservation and droplet growth or shrinkage 5.3.2 Energy conservation and droplet heating or cooling 5.4 Discussion 6 The role of dimensionality on droplet division 6.1 Stability of chemically active droplets in 2D vs. 3D 6.1.1 Stationary droplets in 1D, 2D and 3D 6.1.2 Elongation instability 6.1.3 Pinch-off instability 6.2 Pinch-off in 2D via curvature-dependent chemical reactions 6.2.1 Determining the mean curvature of the droplet interface 6.2.2 Chemical reactions at the interface 6.3 Discussion 7 Conclusion and Outlook A Free energy considerations B Surface tension in multi-component mixtures C Figure details Bibliography
14

Synthetisch interessante Transformationen von Ring-anellierten (E,Z,E)-1,3,5-Hexatrienen / Synthetically interesting transformations of ring-annelated (E,Z,E)-1,3,5-hexatrienes

Essen, Regina von 01 July 2004 (has links)
No description available.
15

Erzeugung von Radikalen aus teilhalogenierten Methan-, Alkohol- und Etherderivaten und deren Reaktionen sowie thermische und chemische Aktivierung von 1-Ethinyl-1-methylcyclopropan in der Gasphase / Formation and degradation of the radicals produced via the reactions of partially halogenated methanes, alcohols and ethers as well as the unimolecular reactions of 1-ethinyl-1-methylcyclopropane induced by thermal and chemical activation in the gas phase

Hold, Markus 30 January 2002 (has links)
No description available.
16

Untersuchung der Reaktion von Wasserstoffatomen mit Sauerstoffmolekülen (H+O2+M → HO2+M) in weiten Druck- und Temperaturbereichen / Investigation of the reaction of hydrogen atoms with oxygen molekules (H+O2+M → HO2+M) in a wide temperature an pressure range

Hahn, Jörg 21 January 2004 (has links)
No description available.
17

Femtosecond mid-infrared spectroscopy of elementary photoinduced reactions

Rini, Matteo 12 December 2003 (has links)
In dieser Arbeit wird Femtosekunden-Spektroskopie im mittleren Infrarot angewandt auf einige der am gründlichsten studierten fotoinduzierten Reaktionen: der Wasserstoff-Protonentransfer im elektronischen angeregten Zustand, für einen intramolekularen und einen intermolekularen Fall, sowie die Isomerisation fotochromer Verbindungen. Elektronische Spektroskopie ist die am häufigsten verwendete Methode zur Untersuchung ultraschneller Reaktionsdynamik in der kondensierten Phase, wobei Übergänge zwischen elektronischen Zuständen der reagierenden molekularen Systeme beobachtet werden. Häufig werden elektronische Übergänge abgetastet, deren Wellenfunktionen delokalisiert sind, so dass kaum ortspezifische Information erhalten wird. Außerdem ist aufgrund der breiten Absorptionslinien, die aus den schnellen Dephasierungszeiten elektronischer Übergänge resultieren, eine verlässliche Interpretation der experimentellen Daten schwierig; dies umso mehr, je komplexer der Reaktion ist, z.B. durch die Anwesenheit verschiedener Isomere oder durch das Zusammenwirken vieler elektronischer Zustände. Femtosekunden-Infrarotspektroskopie wird in dieser Arbeit als leistungsfähige Alternative eingesetzt, um ultraschnelle Reaktionsdynamik zu beobachten, und so den hohen Grad an Korrelation zwischen Infrarotspektren und molekularer Struktur sowie die Vorteile schmaler Bandbreiten IR-aktiver Schwingungsmoden auszunutzen. / In this thesis femtosecond mid-infrared spectroscopy has been applied to the investigation of some of the most thoroughly studied photoinduced reactions: the excited state hydrogen/proton transfer, both in an intramolecular and in an intermolecular case, and the isomerization of photochromic compounds. Electronic spectroscopy is the most commonly used method for ultrafast studies of molecular reaction dynamics in the condensed phase, whereby the electronic states of the reacting molecular systems are monitored. These techniques typically probe electronic transitions occurring between delocalized orbitals and - thus - do not provide site-specific information. Besides, the broad absorption lines resulting from the fast dephasing times of electronic transitions in solutions may hinder a reliable interpretation of the experimental results, especially when the complexity of the reaction increases, due e.g. to the presence of different isomers or to the involvement of numerous electronic states. Femtosecond infrared spectroscopy has been used in this work as a powerful and complementary alternative to probe ultrafast reaction dynamics, exploiting the high degree of correlation between the infrared spectra and the molecular structure and the advantages stemming from the narrow bandwidths of IR-active vibrational modes.
18

Fullerenhaltige Donor-Akzeptor-Blockcopolymere als Additive für organische Bulk-Heterojunction-Solarzellen

Heuken, Maria 30 November 2012 (has links) (PDF)
Fullerenhaltige Bulk-Heterojunction-Solarzellen auf Polymerbasis zeigen derzeit eine geringe Langzeitstabilität, die unter anderem auf der Entmischung der Bulkphasen beruht. In dieser Arbeit wurden daher auf neuartige Weise Blockcopolymere entwickelt, die zur Stabilisierung der Phasen dienen können. Ausgehend von Poly-3-hexylthiophen-Makroinitiatoren wurde ein zweiter Block mit reaktivem Comonomer polymerisiert, das zur Anbindung von reinem Fullerens bzw. von Fullerenderivaten diente. Die fullerenfunktionalisierten Polymere wurden in Modell-Systeme eingemischt und zeigten erste Verbesserungen bezüglich der Phasenstabilisierung.
19

Untersuchung elementarer, plasma-relevanter Ion-Molekül-Reaktionen mit einer GIB-Apparatur

Torrents Martin, Raquel 07 May 2001 (has links) (PDF)
In der vorliegenden Arbeit werden elementare, plasma-relevante Ion-Molekül-Reaktionen in der Gasphase mit einer Guided Ion Beam (GIB)-Apparatur untersucht. Es werden Geschwindigkeitsverteilungen und absolute integrale Reaktionsquerschnitte für die Produkte der Reaktionen 40Ar+/36Ar+ + 40Ar und N2+ + CH4/CD4 für Stoßenergien zwischen 0.1 und 3.5 eV angegeben. Die Ergebnisse lassen Rückschlüsse auf die Dynamik der reaktiven Stöße zu. Bei dem resonanten, symmetrischen Ladungstransferprozeß können 40Ar+-Primär- und Produkt-Ionen aufgrund ihrer unterschiedlichen Flugzeit getrennt nachgewiesen werden. Bei der quasi-resonanten, nicht-symmetrischen Reaktion wird ein isotopenselektierter 36Ar+-Ionenstrahl verwendet, um den Nachweis von 40Ar+-Produkten nicht zu beeinträchtigen. Die Geschwindigkeitsverteilungen dieser Produkte zeigen einen zusätzlichen Anteil von Ionen, die im Schwerpunktsystem vorwärts gestreut werden. Alle Ausgangskanäle der Reaktion N2+ + CX4 (X = H, D) wurden experimentell nachgewiesen. Aus den gemessenen integralen Querschnitten ergibt sich CX3+ als das häufigste Produkt mit einem Anteil von über 85%. Protonierte Produkte werden gegenüber deuterierten bevorzugt. Geschwindigkeitsverteilungen zeigen, daß die Produkte sowohl aus dem Zerfall eines langlebigen Zwischenkomplexes als auch durch einen direkten Prozeß gebildet werden. Oberhalb einer Stoßenergie von 0.5 eV überwiegt der direkte Prozeß. Es wird kein Unterschied im Reaktionsmechanismus von protonierten und deuterierten Produkten gleicher Art festgestellt.
20

Ionenpaarbildung bei Multiphotonenanregung von HCl

Reymann, Michael 23 November 2001 (has links) (PDF)
In der vorliegenden Arbeit wurden Messungen zur Multiphotonenanregung von HCl durchgeführt. Die untersuchten Moleküle wurden dabei in einem Molekularstrahl innerhalb eines Vierpols durch Laserlicht variabler Wellenlänge angeregt. Bei verlustfreier Führung im Vierpol konnten die dabei entstandenen Ionen anhand ihrer Flugzeit bestimmt werden. Die Aufnahme von Wellenlängenspektren für einzelne Massen ermöglichte die Bestimmung der am Zerfall des Moleküls beteiligten resonanten Zwischenzustände. Eine Analyse der Flugzeitspektren der Protonen führte zu genaueren Aussagen über die vorliegenden Zerfallskanäle. Der Schwerpunkt dieser Arbeit wurde dabei auf die Ionenpaarbildung, H+ + Cl-, gelegt.

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