Higher-order molecular properties and excitation energies in single-reference and multireference coupled-cluster theory

Coupled-cluster (CC) theory is one of the most successful approaches in high-accuracy quantum chemistry. The present thesis makes a number of contributions to the determination of molecular properties and excitation energies within the CC framework. The multireference CC (MRCC) method proposed by Mukherjee and coworkers (Mk-MRCC) has been benchmarked within the singles and doubles approximation (Mk-MRCCSD) for molecular equilibrium structures. It is demonstrated that Mk-MRCCSD yields reliable results for multireference cases where single-reference CC methods fail. At the same time, the present work also illustrates that Mk-MRCC still suffers from a number of theoretical problems and sometimes gives rise to results of unsatisfactory accuracy. To determine polarizability tensors and excitation spectra in the MRCC framework, the Mk-MRCC linear-response function has been derived together with the corresponding linear-response equations. Pilot applications show that Mk-MRCC linear-response theory suffers from a severe problem when applied to the calculation of dynamic properties and excitation energies: The Mk-MRCC sufficiency conditions give rise to a redundancy in the Mk-MRCC Jacobian matrix, which entails an artificial splitting of certain excited states. This finding has established a new paradigm in MRCC theory, namely that a convincing method should not only yield accurate energies, but ought to allow for the reliable calculation of dynamic properties as well. In the context of single-reference CC theory, an analytic expression for the dipole Hessian matrix, a third-order quantity relevant to infrared spectroscopy, has been derived and implemented within the CC singles and doubles approximation. The advantages of analytic derivatives over numerical differentiation schemes are demonstrated in some pilot applications.

Higher-order calculations in manifestly Lorentz-invariant baryon chiral perturbation theory

This thesis is concerned with calculations in manifestly Lorentz-invariant baryon chiral perturbation theory beyond order D=4. We investigate two different methods. The first approach consists of the inclusion of additional particles besides pions and nucleons as explicit degrees of freedom. This results in the resummation of an infinite number of higher-order terms which contribute to higher-order low-energy constants in the standard formulation. In this thesis the nucleon axial, induced pseudoscalar, and pion-nucleon form factors are investigated. They are first calculated in the standard approach up to order D=4. Next, the inclusion of the axial-vector meson a_1(1260) is considered. We find three diagrams with an axial-vector meson which are relevant to the form factors. Due to the applied renormalization scheme, however, the contributions of the two loop diagrams vanish and only a tree diagram contributes explicitly. The appearing coupling constant is fitted to experimental data of the axial form factor. The inclusion of the axial-vector meson results in an improved description of the axial form factor for higher values of momentum transfer. The contributions to the induced pseudoscalar form factor, however, are negligible for the considered momentum transfer, and the axial-vector meson does not contribute to the pion-nucleon form factor. The second method consists in the explicit calculation of higher-order diagrams. This thesis describes the applied renormalization scheme and shows that all symmetries and the power counting are preserved. As an application we determine the nucleon mass up to order D=6 which includes the evaluation of two-loop diagrams. This is the first complete calculation in manifestly Lorentz-invariant baryon chiral perturbation theory at the two-loop level. The numerical contributions of the terms of order D=5 and D=6 are estimated, and we investigate their pion-mass dependence. Furthermore, the higher-order terms of the nucleon sigma term are determined with the help of the Feynman-Hellmann theorem.

Higher-order perturbative relativistic corrections to energies and properties

Relativistic effects need to be considered in quantum-chemical calculations on systems including heavy elements or when aiming at high accuracy for molecules containing only lighter elements. In the latter case, consideration of relativistic effects via perturbation theory is an attractive option. Among the available techniques, Direct Perturbation Theory (DPT) in its lowest order (DPT2) has become a standard tool for the calculation of relativistic corrections to energies and properties.In this work, the DPT treatment is extended to the next order (DPT4). It is demonstrated that the DPT4 correction can be obtained as a second derivative of the energy with respect to the relativistic perturbation parameter. Accordingly, differentiation of a suitable Lagrangian, thereby taking into account all constraints on the wave function, provides analytic expressions for the fourth-order energy corrections. The latter have been implemented at the Hartree-Fock level and within second-order Møller-Plesset perturbaton theory using standard analytic second-derivative techniques into the CFOUR program package. For closed-shell systems, the DPT4 corrections consist of higher-order scalar-relativistic effects as well as spin-orbit corrections with the latter appearing here for the first time in the DPT series.Relativistic corrections are reported for energies as well as for first-order electrical properties and compared to results from rigorous four-component benchmark calculations in order to judge the accuracy and convergence of the DPT expansion for both the scalar-relativistic as well as the spin-orbit contributions. Additionally, the importance of relativistic effects to the bromine and iodine quadrupole-coupling tensors is investigated in a joint experimental and theoretical study concerning the rotational spectra of CH2BrF, CHBrF2, and CH2FI.

Quadraturformeln für das Qualokationsverfahren

Im Mittelpunkt dieser Arbeit steht Beweis der Existenz- und Eindeutigkeit von Quadraturformeln, die für das Qualokationsverfahren geeignet sind. Letzteres ist ein von Sloan, Wendland und Chandler entwickeltes Verfahren zur numerischen Behandlung von Randintegralgleichungen auf glatten Kurven (allgemeiner: periodische Pseudodifferentialgleichungen). Es erreicht die gleichen Konvergenzordnungen wie das Petrov-Galerkin-Verfahren, wenn man durch den Operator bestimmte Quadraturformeln verwendet. Zunächst werden die hier behandelten Pseudodifferentialoperatoren und das Qualokationsverfahren vorgestellt. Anschließend wird eine Theorie zur Existenz und Eindeutigkeit von Quadraturformeln entwickelt. Ein wesentliches Hilfsmittel hierzu ist die hier bewiesene Verallgemeinerung eines Satzes von Nürnberger über die Existenz und Eindeutigkeit von Quadraturformeln mit positiven Gewichten, die exakt für Tschebyscheff-Räume sind. Es wird schließlich gezeigt, dass es stets eindeutig bestimmte Quadraturformeln gibt, welche die in den Arbeiten von Sloan und Wendland formulierten Bedingungen erfüllen. Desweiteren werden 2-Punkt-Quadraturformeln für so genannte einfache Operatoren bestimmt, mit welchen das Qualokationsverfahren mit einem Testraum von stückweise konstanten Funktionen eine höhere Konvergenzordnung hat. Außerdem wird gezeigt, dass es für nicht-einfache Operatoren im Allgemeinen keine Quadraturformel gibt, mit der die Konvergenzordnung höher als beim Petrov-Galerkin-Verfahren ist. Das letzte Kapitel beinhaltet schließlich numerische Tests mit Operatoren mit konstanten und variablen Koeffizienten, welche die theoretischen Ergebnisse der vorangehenden Kapitel bestätigen.

New path integral simulation algorithms and their application to creep in the quantum sine-Gordon chain

A path integral simulation algorithm which includes a higher-order Trotter approximation (HOA)is analyzed and compared to an approach which includes the correct quantum mechanical pair interaction (effective Propagator (EPr)). It is found that the HOA algorithmconverges to the quantum limit with increasing Trotter number P as P^{-4}, while the EPr algorithm converges as P^{-2}.The convergence rate of the HOA algorithm is analyzed for various physical systemssuch as a harmonic chain,a particle in a double-well potential, gaseous argon, gaseous helium and crystalline argon. A new expression for the estimator for the pair correlation function in the HOA algorithm is derived. A new path integral algorithm, the hybrid algorithm, is developed.It combines an exact treatment of the quadratic part of the Hamiltonian and thehigher-order Trotter expansion techniques.For the discrete quantum sine-Gordon chain (DQSGC), it is shown that this algorithm works more efficiently than all other improved path integral algorithms discussed in this work. The new simulation techniques developed in this work allow the analysis of theDQSGC and disordered model systems in the highly quantum mechanical regime using path integral molecular dynamics (PIMD)and adiabatic centroid path integral molecular dynamics (ACPIMD).The ground state phonon dispersion relation is calculated for the DQSGC by the ACPIMD method.It is found that the excitation gap at zero wave vector is reduced by quantum fluctuations. Two different phases exist: One phase with a finite excitation gap at zero wave vector, and a gapless phase where the excitation gap vanishes.The reaction of the DQSGC to an external driving force is analyzed at T=0.In the gapless phase the system creeps if a small force is applied, and in the phase with a gap the system is pinned. At a critical force, the systems undergo a depinning transition in both phases and flow is induced. The analysis of the DQSGC is extended to models with disordered substrate potentials. Three different cases are analyzed: Disordered substrate potentials with roughness exponent H=0, H=1/2,and a model with disordered bond length. For all models, the ground state phonon dispersion relation is calculated.

Use of computer algebra in the calculation of Feynman diagrams

The increasing precision of current and future experiments in high-energy physics requires a likewise increase in the accuracy of the calculation of theoretical predictions, in order to find evidence for possible deviations of the generally accepted Standard Model of elementary particles and interactions. Calculating the experimentally measurable cross sections of scattering and decay processes to a higher accuracy directly translates into including higher order radiative corrections in the calculation. The large number of particles and interactions in the full Standard Model results in an exponentially growing number of Feynman diagrams contributing to any given process in higher orders. Additionally, the appearance of multiple independent mass scales makes even the calculation of single diagrams non-trivial. For over two decades now, the only way to cope with these issues has been to rely on the assistance of computers. The aim of the xloops project is to provide the necessary tools to automate the calculation procedures as far as possible, including the generation of the contributing diagrams and the evaluation of the resulting Feynman integrals. The latter is based on the techniques developed in Mainz for solving one- and two-loop diagrams in a general and systematic way using parallel/orthogonal space methods. These techniques involve a considerable amount of symbolic computations. During the development of xloops it was found that conventional computer algebra systems were not a suitable implementation environment. For this reason, a new system called GiNaC has been created, which allows the development of large-scale symbolic applications in an object-oriented fashion within the C++ programming language. This system, which is now also in use for other projects besides xloops, is the main focus of this thesis. The implementation of GiNaC as a C++ library sets it apart from other algebraic systems. Our results prove that a highly efficient symbolic manipulator can be designed in an object-oriented way, and that having a very fine granularity of objects is also feasible. The xloops-related parts of this work consist of a new implementation, based on GiNaC, of functions for calculating one-loop Feynman integrals that already existed in the original xloops program, as well as the addition of supplementary modules belonging to the interface between the library of integral functions and the diagram generator.

Synthetical engineering of supramolecular properties of large polycyclic aromatic hydrocarbons

An important property for devices is the charge-carrier mobility values for discotic organic materials like hexa-peri-hexabenzocoronenes. A close relation exists between the degree of their columnar self-arrangement of the molecules and their mobilities. Within this first step an induction of a higher order via hydrogen-bonding was considered, which mainly pointed towards the improvement of the intracolumnar stacking of the materials. For the analytics a broad range of methods was used including differential scanning calorimetry (DSC), wide-angle X-ray diffractometry (WAXS), solid-state NMR spectroscopy and scanning tunneling microscopy (STM). Indeed, a specific influence of the hydrogen-bonds could be identified, although in several cases by the cost of a severe reduction of solubility and processability. This effect was dampened by the addition of a long alkyl chain next to the hydrogen-bond exerting functional group, which resulted in an improved columnar arrangement by retention of processability. In contrast to the before mentioned example of inducing a higher intracolumnar order by hydrogen-bonding, the focus was also be set upon larger aromatic systems. The charge-carrier mobility is also in close relation to the size of the aromatic core and larger π-areas are expected to lead to improved mobilities. For photovoltaic applications a high extinction coefficient over a broad range of the spectrum is favorable, which can also be achieved by enlarging the aromatic core component. In addition the stronger π-interactions between the aromatic core components should yield an improved columnar stability and order. However the strengthening of the π-interactions between the aromatic core components led to a reduction of the solubility and the processability due to the stronger aggregation of the molecules. This required the introduction of efficiently solubilizing features in terms of long alkyl chains in the corona of the aromatic entity, in combination of a distortion of the aromatic core moiety by bulky tert-butyl groups. By this approach not only the processing and cleaning of the materials with standard laboratory techniques became possible, but moreover the first structure-rich UV/vis and a resolved 1H-NMR spectra for an aromatic system two times larger than hexa-peri-hexabenzocoronene were recorded. The bulk properties in an extruded fiber as well as on the surface showed a columnar self-assembly including a phase in which a homeotropic alignment on a substrate was observed, which turns the material into an interesting candidate for future applications in electronic devices.

Verwendung von Präzisionsmessungen zur Eingrenzung von Effekten jenseits des Standardmodells mittels eines effektiven feldtheoretischen Zugangs

Es gibt kaum eine präzisere Beschreibung der Natur als die durch das Standardmodell der Elementarteilchen (SM). Es ist in der Lage bis auf wenige Ausnahmen, die Physik der Materie- und Austauschfelder zu beschreiben. Dennoch ist man interessiert an einer umfassenderen Theorie, die beispielsweise auch die Gravitation mit einbezieht, Neutrinooszillationen beschreibt, und die darüber hinaus auch weitere offene Fragen klärt. Um dieser Theorie ein Stück näher zu kommen, befasst sich die vorliegende Arbeit mit einem effektiven Potenzreihenansatz zur Beschreibung der Physik des Standardmodells und neuer Phänomene. Mit Hilfe eines Massenparameters und einem Satz neuer Kopplungskonstanten wird die Neue Physik parametrisiert. In niedrigster Ordnung erhält man das bekannte SM, Terme höherer Ordnung in der Kopplungskonstanten beschreiben die Effekte jenseits des SMs. Aus gewissen Symmetrie-Anforderungen heraus ergibt sich eine definierte Anzahl von effektiven Operatoren mit Massendimension sechs, die den hier vorgestellten Rechnungen zugrunde liegen. Wir berechnen zunächst für eine bestimmte Auswahl von Prozessen zugehörige Zerfallsbreiten bzw. Wirkungsquerschnitte in einem Modell, welches das SM um einen einzigen neuen effektiven Operator erweitertet. Unter der Annahme, dass der zusätzliche Beitrag zur Observablen innerhalb des experimentellen Messfehlers ist, geben wir anhand von vorliegenden experimentellen Ergebnissen aus leptonischen und semileptonischen Präzisionsmessungen Ausschlussgrenzen der neuen Kopplungen in Abhängigkeit von dem Massenparameter an. Die hier angeführten Resultate versetzen Physiker zum Einen in die Lage zu beurteilen, bei welchen gemessenen Observablen eine Erhöhung der Präzision sinnvoll ist, um bessere Ausschlussgrenzen angeben zu können. Zum anderen erhält man einen Anhaltspunkt, welche Prozesse im Hinblick auf Entdeckungen Neuer Physik interessant sind.

Renormalization of fermion mixing

Precision measurements of phenomena related to fermion mixing require the inclusion of higher order corrections in the calculation of corresponding theoretical predictions. For this, a complete renormalization scheme for models that allow for fermion mixing is highly required. The correct treatment of unstable particles makes this task difficult and yet, no satisfactory and general solution can be found in the literature. In the present work, we study the renormalization of the fermion Lagrange density with Dirac and Majorana particles in models that involve mixing. The first part of the thesis provides a general renormalization prescription for the Lagrangian, while the second one is an application to specific models. In a general framework, using the on-shell renormalization scheme, we identify the physical mass and the decay width of a fermion from its full propagator. The so-called wave function renormalization constants are determined such that the subtracted propagator is diagonal on-shell. As a consequence of absorptive parts in the self-energy, the constants that are supposed to renormalize the incoming fermion and the outgoing antifermion are different from the ones that should renormalize the outgoing fermion and the incoming antifermion and not related by hermiticity, as desired. Instead of defining field renormalization constants identical to the wave function renormalization ones, we differentiate the two by a set of finite constants. Using the additional freedom offered by this finite difference, we investigate the possibility of defining field renormalization constants related by hermiticity. We show that for Dirac fermions, unless the model has very special features, the hermiticity condition leads to ill-defined matrix elements due to self-energy corrections of external legs. In the case of Majorana fermions, the constraints for the model are less restrictive. Here one might have a better chance to define field renormalization constants related by hermiticity. After analysing the complete renormalized Lagrangian in a general theory including vector and scalar bosons with arbitrary renormalizable interactions, we consider two specific models: quark mixing in the electroweak Standard Model and mixing of Majorana neutrinos in the seesaw mechanism. A counter term for fermion mixing matrices can not be fixed by only taking into account self-energy corrections or fermion field renormalization constants. The presence of unstable particles in the theory can lead to a non-unitary renormalized mixing matrix or to a gauge parameter dependence in its counter term. Therefore, we propose to determine the mixing matrix counter term by fixing the complete correction terms for a physical process to experimental measurements. As an example, we calculate the decay rate of a top quark and of a heavy neutrino. We provide in each of the chosen models sample calculations that can be easily extended to other theories.

Factorization method and irregular inclusions in electrical impedance tomography

In electrical impedance tomography, one tries to recover the conductivity inside a physical body from boundary measurements of current and voltage. In many practically important situations, the investigated object has known background conductivity but it is contaminated by inhomogeneities. The factorization method of Andreas Kirsch provides a tool for locating such inclusions. Earlier, it has been shown that under suitable regularity conditions positive (or negative) inhomogeneities can be characterized by the factorization technique if the conductivity or one of its higher normal derivatives jumps on the boundaries of the inclusions. In this work, we use a monotonicity argument to generalize these results: We show that the factorization method provides a characterization of an open inclusion (modulo its boundary) if each point inside the inhomogeneity has an open neighbourhood where the perturbation of the conductivity is strictly positive (or negative) definite. In particular, we do not assume any regularity of the inclusion boundary or set any conditions on the behaviour of the perturbed conductivity at the inclusion boundary. Our theoretical findings are verified by two-dimensional numerical experiments.

Towards a new test of time dilation: Laser spectroscopy on lithium ions stored at a velocity of 33.8 % of the speed of light

The subject of the presented thesis is the accurate measurement of time dilation, aiming at a quantitative test of special relativity. By means of laser spectroscopy, the relativistic Doppler shifts of a clock transition in the metastable triplet spectrum of ^7Li^+ are simultaneously measured with and against the direction of motion of the ions. By employing saturation or optical double resonance spectroscopy, the Doppler broadening as caused by the ions' velocity distribution is eliminated. From these shifts both time dilation as well as the ion velocity can be extracted with high accuracy allowing for a test of the predictions of special relativity. A diode laser and a frequency-doubled titanium sapphire laser were set up for antiparallel and parallel excitation of the ions, respectively. To achieve a robust control of the laser frequencies required for the beam times, a redundant system of frequency standards consisting of a rubidium spectrometer, an iodine spectrometer, and a frequency comb was developed. At the experimental section of the ESR, an automated laser beam guiding system for exact control of polarisation, beam profile, and overlap with the ion beam, as well as a fluorescence detection system were built up. During the first experiments, the production, acceleration and lifetime of the metastable ions at the GSI heavy ion facility were investigated for the first time. The characterisation of the ion beam allowed for the first time to measure its velocity directly via the Doppler effect, which resulted in a new improved calibration of the electron cooler. In the following step the first sub-Doppler spectroscopy signals from an ion beam at 33.8 %c could be recorded. The unprecedented accuracy in such experiments allowed to derive a new upper bound for possible higher-order deviations from special relativity. Moreover future measurements with the experimental setup developed in this thesis have the potential to improve the sensitivity to low-order deviations by at least one order of magnitude compared to previous experiments; and will thus lead to a further contribution to the test of the standard model.

Magnetization dynamics in spin valves

Key technology applications like magnetoresistive sensors or the Magnetic Random Access Memory (MRAM) require reproducible magnetic switching mechanisms. i.e. predefined remanent states. At the same time advanced magnetic recording schemes push the magnetic switching time into the gyromagnetic regime. According to the Landau-Lifschitz-Gilbert formalism, relevant questions herein are associated with magnetic excitations (eigenmodes) and damping processes in confined magnetic thin film structures.rnObjects of study in this thesis are antiparallel pinned synthetic spin valves as they are extensively used as read heads in today’s magnetic storage devices. In such devices a ferromagnetic layer of high coercivity is stabilized via an exchange bias field by an antiferromagnet. A second hard magnetic layer, separated by a non-magnetic spacer of defined thickness, aligns antiparallel to the first. The orientation of the magnetization vector in the third ferromagnetic NiFe layer of low coercivity - the freelayer - is then sensed by the Giant MagnetoResistance (GMR) effect. This thesis reports results of element specific Time Resolved Photo-Emission Electron Microscopy (TR-PEEM) to image the magnetization dynamics of the free layer alone via X-ray Circular Dichroism (XMCD) at the Ni-L3 X-ray absorption edge.rnThe ferromagnetic systems, i.e. micron-sized spin valve stacks of typically deltaR/R = 15% and Permalloy single layers, were deposited onto the pulse leading centre stripe of coplanar wave guides, built in thin film wafer technology. The ferromagnetic platelets have been applied with varying geometry (rectangles, ellipses and squares), lateral dimension (in the range of several micrometers) and orientation to the magnetic field pulse to study the magnetization behaviour in dependence of these magnitudes. The observation of magnetic switching processes in the gigahertz range became only possible due to the joined effort of producing ultra-short X-ray pulses at the synchrotron source BESSY II (operated in the so-called low-alpha mode) and optimizing the wave guide design of the samples for high frequency electromagnetic excitation (FWHM typically several 100 ps). Space and time resolution of the experiment could be reduced to d = 100 nm and deltat = 15 ps, respectively.rnIn conclusion, it could be shown that the magnetization dynamics of the free layer of a synthetic GMR spin valve stack deviates significantly from a simple phase coherent rotation. In fact, the dynamic response of the free layer is a superposition of an averaged critically damped precessional motion and localized higher order spin wave modes. In a square platelet a standing spin wave with a period of 600 ps (1.7 GHz) was observed. At a first glance, the damping coefficient was found to be independent of the shape of the spin-valve element, thus favouring the model of homogeneous rotation and damping. Only by building the difference in the magnetic rotation between the central region and the outer rim of the platelet, the spin wave becomes visible. As they provide an additional efficient channel for energy dissipation, spin waves contribute to a higher effective damping coefficient (alpha = 0.01). Damping and magnetic switching behaviour in spin valves thus depend on the geometry of the element. Micromagnetic simulations reproduce the observed higher-order spin wave mode.rnBesides the short-run behaviour of the magnetization of spin valves Permalloy single layers with thicknesses ranging from 3 to 40 nm have been studied. The phase velocity of a spin wave in a 3 nm thick ellipse could be determined to 8.100 m/s. In a rectangular structure exhibiting a Landau-Lifschitz like domain pattern, the speed of the field pulse induced displacement of a 90°-Néel wall has been determined to 15.000 m/s.rn

Structure formation as studied by EPR spectroscopy: From simple solutions to nanoparticles

In this thesis, three nitroxide based ionic systems were used to investigate structure and dynamics of their respective solutions in mixed solvents by means of electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) spectroscopy at X- and W-band (9.5 and 94.5 GHz, respectively). rnFirst, the solvation of the inorganic radical Fremy’s salt (K2ON(SO3)2) in isotope substituted binary solvent mixtures (methanol/water) was investigated by means of high-field (W-band) pulse ENDOR spectroscopy and molecular dynamics (MD) simulations. From the analysis of orientation-selective 1H and 2H ENDOR spectra the principal components of the hyperfine coupling (hfc) tensor for chemically different protons (alcoholic methyl vs. exchangeable protons) were obtained. The methyl protons of the organic solvent approach with a mean distance of 3.5 Å perpendicular to the approximate plane spanned by ON(S)2 of the probe molecule. Exchangeable protons were found to be distributed isotropically, approaching closest to Fremy’s salt from the hydrogen-bonded network around the sulfonate groups. The distribution of exchangeable and methyl protons as found in MD simulations is in full agreement with the ENDOR results. The solvation was found to be similar for the studied solvent ratios between 1:2.3 and 2.3:1 and dominated by an interplay of H-bond (electrostatic) interactions and steric considerations with the NO group merely involved into H-bonds.rnFurther, the conformation of spin labeled poly(diallyldimethylammonium chloride) (PDADMAC) solutions in aqueous alcohol (methanol, ethanol, n-propanol, ethylene glycol, glycerol) mixtures in dependence of divalent sodium sulfate was investigated with double electron-electron resonance (DEER) spectroscopy. The DEER data was analyzed using the worm-like chain model which suggests that in organic-water solvent mixtures the polymer backbones are preferentially solvated by the organic solvent. We found a less serve impact on conformational changes due to salt than usually predicted in polyelectrolyte theory which stresses the importance of a delicate balance of hydrophobic and electrostatic interactions, in particular in the presence of organic solvents.rnFinally, the structure and dynamics of miniemulsions and polymerdispersions prepared with anionic surfactants, that were partially replaced by a spin labeled fatty acid in presence and absence of a lanthanide beta-diketonate complex was characterized by CW EPR spectroscopy. Such miniemulsions form multilayers with the surfactant head group bound to the lanthanide ion. Beta-diketonates were formerly used as NMR shift reagents and nowadays find application as luminescent materials in OLEDs and LCDs and as contrast agent in MRT. The embedding of the complex into a polymer matrix results in an easy processable material. It was found that the structure formation takes place in miniemulsion and is preserved during polymerization. For surfactants with carboxyl-head group a higher order of the alkyl chains and less lateral diffusion is found than for sulfat-head groups, suggesting a more uniform and stronger coordination to the metal ion. The stability of these bilayers depends on the temperature and the used surfactant which should be considered for the used polymerization temperature if a maximum output of the structured regions is wished.

Near-field mediated enhancement effects on plasmonic nanostructures

In dieser Arbeit wird eine detaillierte Untersuchung und Charakterisierung der Zwei-Photonen-induzierten Fluoreszenzverstärkung von organischen Farbstoffen auf plasmonischen Nanostrukturen vorgestellt. Diese Fluoreszenzverstärkung ist insbesondere für hochaufgelöste Fluoreszenzmikroskopie und Einzelmolekülspektroskopie von großer Bedeutung. Durch die Zwei-Photonen-Anregung resultiert eine Begrenzung des Absorptionsprozesses auf das fokale Volumen. In Kombination mit dem elektrischen Nahfeld der Nanostrukturen als Anregungsquelle entsteht eine noch stärkere Verringerung des Anregungsvolumens auf eine Größe unterhalb der Beugungsgrenze. Dies erlaubt die selektive Messung ausgewählter Farbstoffe. Durch die Herstellung der Nanopartikel mittels Kolloidlithografie wird eine definierte, reproduzierbare Geometrie erhalten. Polymermultischichten dienen als Abstandshalter, um die Farbstoffe an einer exakten Distanz zum Metall zu positionieren. Durch die kovalente Anbindung des Farbstoffs an die oberste Schicht wird eine gleichmäßige Verteilung des Farbstoffs in geringer Konzentration erhalten. rnEs wird eine Verstärkung der Fluoreszenz um den Faktor 30 für Farbstoffe auf Goldellipsen detektiert, verglichen mit Farbstoffen außerhalb des Nahfelds. Sichelförmige Nanostrukturen erzeugen eine Verstärkung von 120. Dies belegt, dass das Ausmaß der Fluoreszenzverstärkung entscheidend von der Stärke des elektrischen Nahfelds der Nanostruktur abhängt. Auch das Material der Nanostruktur ist hierbei von Bedeutung. So erzeugen Silberellipsen eine 1,5-fach höhere Fluoreszenzverstärkung als identische Goldellipsen. Distanzabhängige Fluoreszenzmessungen zeigen, dass die Zwei-Photonen-angeregte Fluoreszenzverstärkung an strukturspezifischen Abständen zum Metall maximiert wird. Elliptische Strukturen zeigen ein Maximum bei einem Abstand von 8 nm zum Metall, wohingegen bei sichelförmigen Nanostrukturen die höchste Fluoreszenzintensität bei 12 nm gemessen wird. Bei kleineren Abständen unterliegt der Farbstoff einem starken Löschprozess, sogenanntes Quenching. Dieses konkurriert mit dem Verstärkungsprozess, wodurch es zu einer geringen Nettoverstärkung kommt. Hat die untersuchte Struktur Dimensionen größer als das Auflösungsvermögen des Mikroskops, ist eine direkte Visualisierung des elektrischen Nahfelds der Nanostruktur möglich. rnrnEin weiterer Fokus dieser Arbeit lag auf der Herstellung neuartiger Nanostrukturen durch kolloidlithografische Methoden. Gestapelte Dimere sichelförmiger Nanostrukturen mit exakter vertikaler Ausrichtung und einem Separationsabstand von etwa 10 nm wurden hergestellt. Die räumliche Nähe der beiden Strukturen führt zu einem Kopplungsprozess, der neue optische Resonanzen hervorruft. Diese können als Superpositionen der Plasmonenmoden der einzelnen Sicheln beschrieben werden. Ein Hybridisierungsmodell wird angewandt, um die spektralen Unterschiede zu erklären. Computersimulationen belegen die zugrunde liegende Theorie und erweitern das Modell um experimentell nicht aufgelöste Resonanzen. rnWeiterhin wird ein neuer Herstellungsprozess für sichelförmige Nanostrukturen vorgestellt, der eine präzise Formanpassung ermöglicht. Hierdurch kann die Lage der Plasmonenresonanz exakt justiert werden. Korrelationen der geometrischen Daten mit den Resonanzwellenlängen tragen zum grundlegenden Verständnis der Plasmonenresonanzen bei. Die vorgestellten Resultate wurden mittels Computersimulationen verifiziert. Der Fabrikationsprozess erlaubt die Herstellung von Dimeren sichelförmiger Nanostrukturen in einer Ebene. Durch die räumliche Nähe überlappen die elektrischen Nahfelder, wodurch es zu kopplungs-induzierten Shifts der Plasmonenresonanzen kommt. Der Unterschied zu theoretisch berechneten ungekoppelten Nanosicheln kann auch bei den gegenüberliegenden sichelförmigen Nanostrukturen mit Hilfe des Plasmonenhybridisierungsmodells erklärt werden.

Supersymmetry searches in the single lepton final state with the ATLAS detector

This thesis presents an analysis for the search of Supersymmetry with the ATLAS detector at the LHC. The final state with one lepton, several coloured particles and large missing transverse energy was chosen. Particular emphasis was placed on the optimization of the requirements for lepton identification. This optimization showed to be particularly useful when combining with multi-lepton selections. The systematic error associated with the higher order QCD diagrams in Monte Carlo production is given particular focus. Methods to verify and correct the energy measurement of hadronic showers are developed. Methods for the identification and removal of mismeasurements caused by the detector are found in the single muon and four jet environment are applied. A new detector simulation system is shown to provide good prospects for future fast Monte Carlo production. The analysis was performed for $35pb^{-1}$ and no significant deviation from the Standard Model is seen. Exclusion limits subchannel for minimal Supergravity. Previous limits set by Tevatron and LEP are extended.