This thesis deals with exciton relaxation processes in thin polycrystalline films and matrix-isolated molecules of the perylene derivatives PTCDA (3,4,9,10-perylenetetracarboxylic dianhydride) and MePTCDI (N,N'-dimethylperylene-3,4,9,10-dicarboximide). Using femtosecond pump-probe spectroscopy, transient absorption spectra, excitonic relaxation in the lowest excited state subsequent to excitation, and exciton-exciton interaction and annihilation at high excitation densities have been addressed. Transient absorption spectroscopy in the range 1.2eV-2.6eV has been applied to thin polycrystalline films of PTCDA and MePTCDI and to solid solutions of PTCDA and MePTCDI molecules (monomers) in a SiO2 matrix. We are able to ascribe the respective signal contributions to ground state bleaching, stimulated emission, and excited state absorption. Both systems exhibit broad excited-state absorption features below 2.0eV, with dominant peaks between 1.8eV and 2.0eV. The monomer spectra can be consistently explained by the results of quantum-chemical calculations on single molecules, and the respective experimental polarization anisotropies for the two major transitions agree with the calculated polarizations. Dimer calculations allow to qualitatively understand the trends visible in the experimental results from monomers to thin films. The broad excited state absorption band between 1.8eV and 2.0eV allows to probe the population dynamics in the first excited state of thin films. We show that excitons created at the Gamma point relax towards the border of the Brillouin zone on a 100fs time scale in both systems. Excitonic relaxation is accelerated by increase of temperature and/or excitation density, which is attributed to stimulated phonon emission during relaxation in k-space. Lower and upper limits of the intraband relaxation time constants are 25fs (resolution limit) and 250fs (100fs) for PTCDA (MePTCDI). These values agree with the upper limit for the intraband relaxation time of 10ps, evaluated from time-resolved luminescence measurements. While the luminescence anisotropy is in full accordance with the predictions made by a luminescence anisotropy model being consistent with the exciton model of Davydov-split states, the pump-probe anisotropy calls for an explanation beyond the models presently available. At excitation densities 10^(19)cm^(-3), the major de-excitation mechanism for the relaxed excitons is exciton-exciton annihilation, resulting in a strongly reduced exciton life time. Three different models for the microscopic behavior have been tested: a diffusion-limited annihilation model in both three and one dimensions (with diffusion constant D as fit parameter) as well as a long-range single-step Förster-type annihilation model (with Förster radius RF as fit parameter). For PTCDA, the latter two, being structurally equivalent, allow to fit a set of multiexponential decay curves for multiple initial exciton densities with high precision. In contrast, the three-dimensional diffusion-limited model is clearly inferior. For all three models, we extract annihilation rates, diffusion constants and diffusion lengths (or Förster radii), for both room and liquid helium temperature. Temperature dependence and orders of magnitude of the obtained parameters D or RF correspond to the expectations. For MePTCDI, the 1D and the Förster model are in good agreement for a smaller interval of excitation densities. For a initial exciton densities higher than 5 x 10^(19)cm^(-3), the 3D model performs significantly better than the other two.

Für die Simulation technischer Bauteile mit Hilfe der Finite-Elemente-Methode (FEM) werden tensorielle Stoffgesetze benötigt, die zu einem beliebigen dreidimensionalen Verzerrungszustand und gegebenenfalls der Belastungsvorgeschichte und -geschwindigkeit des Materials die zugehörige Spannungsantwort liefern. Die Entwicklung derart komplexer Materialmodelle verläuft oftmals über Zwischenstufen, die zunächst nur Vorhersagen für den einachsigen Zug-/Druckversuch erlauben. Zur automatischen Verallgemeinerung solcher eindimensionaler Materialbeschreibungen zu vollständig dreidimensionalen Stoffgesetzen für die Finite-Elemente-Methode wird im Rahmen dieser Arbeit das Konzept repräsentativer Raumrichtungen vorgeschlagen, welches auf der Integration einachsiger Spannungszustände über eine diskrete Anzahl gleichmäßig verteilter (repräsentativer) Raumrichtungen basiert. Zur Untersuchung der grundlegenden Eigenschaften des Algorithmus wurden verschiedene inelastische tensorielle Beispielstoffgesetze herangezogen, deren eindimensionale Formulierung als Eingangsmodell für die repräsentativen Raumrichtungen dient. Hierbei zeigt sich, dass die wesentlichen Materialeigenschaften des jeweiligen uniaxialen Eingangsmodells bei der Verallgemeinerung vollständig erhalten bleiben. Weiterhin werden einige wichtige Effekte vom Konzept automatisch generiert, wie z. B. die anisotrope Entfestigung technischer Gummiwerkstoffe oder die formative Verfestigung metallischer Werkstoffe, was eine realitätsnahe Simulation dieser Materialklassen ohne zusätzlichen Arbeitsaufwand erlaubt. Das Konzept wurde zusätzlich auf Stoffgesetze angewendet, die ausschließlich in Form einer eindimensionalen Materialbeschreibung vorliegen und somit konkrete Anwendungsfällle darstellen. Darüber hinaus wurden für einige ausgewählte Stoffgesetze in repräsentativen Raumrichtungen Vergleiche mit Ergebnissen aus experimentellen Versuchen vorgenommen, wobei sich stets eine gute Übereinstimmung zwischen Experiment und Simulation ergibt. Das Konzept repräsentativer Raumrichtungen wurde in die zwei kommerziellen Finite-Elemente-Programme MSC.Marc und ABAQUS implementiert. Hiermit können Simulationen inhomogener Verzerrungs- und Spannungsverteilungen durchgeführt werden, obwohl das zugrunde liegende Stoffgesetz lediglich einachsige Spannungszustände beschreibt. In diesem Zusammenhang werden verschiedene Methoden vorgestellt, mit deren Hilfe die Effizienz einer FEM-Simulation erheblich gesteigert werden kann. Dies betrifft zum einen die Generierung einer gleichmäßigen Verteilung von repräsentativen Raumrichtungen mit Hilfe eines numerischen Algorithmus zur Simulation sich abstoßender elektrischer Punktladungen auf der Kugeloberfläche. Zum anderen besteht die Möglichkeit, die einzelnen Sätze von repräsentativen Raumrichungen in den Gaußpunkten eines finiten Elementes unterschiedlich zueinander auszurichten, was bei gleichbleibendem Rechenaufwand eine beträchtliche Erhöhung der Rechengenauigkeit erlaubt. / The simulation of technical components using the finite element method (FEM) requires tensorial constitutive models which describe the complete relation between a given three-dimensional state of strain (in some cases also the loading history and strain rate) and the corresponding state of stress. The development of such complex material models often leads to an intermediate stage that enables the prediction of uniaxial tension and compression only. The automatic generalization of those one-dimensional material descriptions to complete three-dimensional constitutive models for the finite element method can be accomplished by using the concept of representative directions which is based on the integration of uniaxial stresses over a discrete number of uniformly distributed (representative) directions in space. In order to investigate the fundamental characteristics of the algorithm several inelastic tensorial constitutive models were used, whose one-dimensional formulation serves as the input model for the use within the representative directions. In this context it becomes evident that the essential material properties of the respective uniaxial input model are completely preserved during the process of generalization. Furthermore, some important effects are produced automatically by the concept such as the anisotropic stress softening of technical rubber materials or the distortional hardening of metallic materials, which enables a realistic simulation of those material classes without spending additional effort. The concept was also applied to material models that are available in form of a one-dimensional material description only, so that these can be regarded as concrete applications. In addition, some of the material models in representative directions were compared to experimental data, whereas a good agreement between measurement and simulation can be noticed. The concept of representative directions has been implemented into the commercial finite element programs MSC.Marc and ABAQUS. This enables simulations of inhomogeneous strain and stress distributions even though the underlying material model describes uniaxial loading processes only. In this context, several methods are introduced which can be applied to increase the efficiency of a finite element simulation to a great extent. On the one hand this affects the generation of a uniform distribution of representative directions using a numerical algorithm simulating the repulsion of electric charges on the surface of a sphere. On the other hand, it is possible to adjust the sets of representative directions at the integration points of a finite element differently, which leads to an increasing computational accuracy at constant computational effort.

This thesis deals with exciton relaxation processes in thin polycrystalline films and matrix-isolated molecules of the perylene derivatives PTCDA (3,4,9,10-perylenetetracarboxylic dianhydride) and MePTCDI (N,N'-dimethylperylene-3,4,9,10-dicarboximide). Using femtosecond pump-probe spectroscopy, transient absorption spectra, excitonic relaxation in the lowest excited state subsequent to excitation, and exciton-exciton interaction and annihilation at high excitation densities have been addressed. Transient absorption spectroscopy in the range 1.2eV-2.6eV has been applied to thin polycrystalline films of PTCDA and MePTCDI and to solid solutions of PTCDA and MePTCDI molecules (monomers) in a SiO2 matrix. We are able to ascribe the respective signal contributions to ground state bleaching, stimulated emission, and excited state absorption. Both systems exhibit broad excited-state absorption features below 2.0eV, with dominant peaks between 1.8eV and 2.0eV. The monomer spectra can be consistently explained by the results of quantum-chemical calculations on single molecules, and the respective experimental polarization anisotropies for the two major transitions agree with the calculated polarizations. Dimer calculations allow to qualitatively understand the trends visible in the experimental results from monomers to thin films. The broad excited state absorption band between 1.8eV and 2.0eV allows to probe the population dynamics in the first excited state of thin films. We show that excitons created at the Gamma point relax towards the border of the Brillouin zone on a 100fs time scale in both systems. Excitonic relaxation is accelerated by increase of temperature and/or excitation density, which is attributed to stimulated phonon emission during relaxation in k-space. Lower and upper limits of the intraband relaxation time constants are 25fs (resolution limit) and 250fs (100fs) for PTCDA (MePTCDI). These values agree with the upper limit for the intraband relaxation time of 10ps, evaluated from time-resolved luminescence measurements. While the luminescence anisotropy is in full accordance with the predictions made by a luminescence anisotropy model being consistent with the exciton model of Davydov-split states, the pump-probe anisotropy calls for an explanation beyond the models presently available. At excitation densities 10^(19)cm^(-3), the major de-excitation mechanism for the relaxed excitons is exciton-exciton annihilation, resulting in a strongly reduced exciton life time. Three different models for the microscopic behavior have been tested: a diffusion-limited annihilation model in both three and one dimensions (with diffusion constant D as fit parameter) as well as a long-range single-step Förster-type annihilation model (with Förster radius RF as fit parameter). For PTCDA, the latter two, being structurally equivalent, allow to fit a set of multiexponential decay curves for multiple initial exciton densities with high precision. In contrast, the three-dimensional diffusion-limited model is clearly inferior. For all three models, we extract annihilation rates, diffusion constants and diffusion lengths (or Förster radii), for both room and liquid helium temperature. Temperature dependence and orders of magnitude of the obtained parameters D or RF correspond to the expectations. For MePTCDI, the 1D and the Förster model are in good agreement for a smaller interval of excitation densities. For a initial exciton densities higher than 5 x 10^(19)cm^(-3), the 3D model performs significantly better than the other two.