Mostly new acetylene based monomers were prepared. All monomers were prepared by the means of standard spectroscopic methods. All monomers were successfully polymerized using standard metathesis TaCl5 based catalyst. Prepared polymers were characterized by the means of GPC/GPC-MALLS chromatography and standard spectral methods. Fluorescence properties of all prepared compounds were also studied: quantum fluorescence yields were determined and excitation and emission fluorescence spectra were recorded. Polymerization on modern metathesis Grubbs-Hoveyda catalytic systems of all prepared monomers was also tested. These reactions were only partially successful and only low molecular weight oligomers in mediocre yields were obtained.

In dieser Arbeit wird unter Verwendung des Su-Schrieffer-Heeger-Modells die Dynamik des einfachsten konjugierten Polymers Trans-Polyacetylen in Mean-Field-Approximation untersucht. Dazu wird erstmalig von einer dimerisierten Peierls-Kette im Grundzustand ausgegangen, die durch einen gaußförmigen Laserpuls angeregt wird. Sowohl bei subresonanter Anregung als auch bei Anregungen hoch im Band bilden sich geladene Solitonpaare mit gemischten Gap-Zuständen, für die ein Phasendiagramm in Abhängigkeit vom Mischungsparameter abgeleitet wird. Diese Zustände werden im Rahmen des Takayama-Lin-Liu-Maki-Modells erfolgreich beschrieben.Um einen Ladungstransfer zwischen benachbarten Ketten zu untersuchen, werden die Rechnungen auf zwei gekoppelte Peierls-Ketten ausgedehnt. In Abhängigkeit von der Kopplungsstärke und der Kettenlänge ergibt sich eine Reihe von Grundzustandskonfigurationen. Bei einer Anregung mit einem transversalen Laserpuls findet ein Ladungstransfer zwischen den beiden Ketten mit einer Frequenz statt, die der doppelten Kopplungsstärke entspricht. Zur Einbeziehung der Coulomb-Wechselwirkung der Pi-Elektronen wird das Pariser-Parr-Pople-Modell verwendet. Durch Anpassung an möglichst viele experimentelle Größen wird ein geeigneter Satz von Modell-Parametern berechnet. Die von der Kette aufgenommene Energie und deren Dynamik werden diskutiert. / In the framework of the Su-Schrieffer-Heeger model the dynamics of the most simple conjugated polymer trans-polyacetylene is investigated in mean field approximation. Starting with a dimerized Peierls chain in the ground state, a femtosecond laser pulse with a gaussian enveloppe is applied. For subresonant and high band excitation charged soliton pairs are created and are related to mixed gap states. For different values of the mixing strength a phase diagram can be drawn. The creation of the mixed gap states can be also explained within the continuum approximation with the Takayama-Lin-Liu-Maki model. In order to investigate charge transfer between two Peierls chains, the calculations are extended to a system with two coupled chains. Different ground state configurations occur, depending on the coupling stength and the chain length. In the case of an excitation perpendicular to the chain axis, a strong charge transfer between the chains is observed. Furthermore the Pariser-Parr-Pople model is used to take into account the Coulomb interaction between the Pi-electrons. A model parameter set can be determined by fitting the experimental values. The energy absorbed by the chain and the soliton dynamics are discussed in this model.

In this work a systematic method for determining correlated wavefunctions of extended systems in the ground state as well as in excited states is presented. It allows to fully exploit the power of quantum-chemical programs designed for correlation calculations of finite molecules. Using localized Hartree-Fock (HF) orbitals (both occupied and virtual ones), an effective Hamiltonian which can easily be transferred from finite to infinite systems is built up. Correlation corrections to the matrix elements of the effective Hamiltonian are derived from clusters using an incremental scheme. To treat the correlation effects, multireference configuration interaction (MRCI) calculations with singly and doubly excited configurations (SD) are performed. This way one is able to generate both valence and conduction bands where all correlation effects in the excited states as well as in the ground state of the system are taken into account. An appropriate size-extensivity correction to the MRCI(SD) correlation energies is developed which takes into account the open-shell character of the excited states. This approach is applicable to a wide range of polymers and crystals. In the present work trans-polyacetylene is chosen as a test system. The corresponding band structure is obtained with the correlation of all electrons in the system being included on a very high level of sophistication. The account of correlation effects leads to substantial shifts of the "center-of-mass" positions of the bands (valence bands are shifted upwards and conduction bands downwards) and a flattening of all bands compared to the corresponding HF band structure. The method reaches the quantum-chemical level of accuracy. Further an extention of the above approach to excitons (optical excitations) in crystals is developed which allows to use standard quantum-chemical methods to describe the electron-hole pairs and to finally obtain excitonic bands.

In this work a systematic method for determining correlated wavefunctions of extended systems in the ground state as well as in excited states is presented. It allows to fully exploit the power of quantum-chemical programs designed for correlation calculations of finite molecules. Using localized Hartree-Fock (HF) orbitals (both occupied and virtual ones), an effective Hamiltonian which can easily be transferred from finite to infinite systems is built up. Correlation corrections to the matrix elements of the effective Hamiltonian are derived from clusters using an incremental scheme. To treat the correlation effects, multireference configuration interaction (MRCI) calculations with singly and doubly excited configurations (SD) are performed. This way one is able to generate both valence and conduction bands where all correlation effects in the excited states as well as in the ground state of the system are taken into account. An appropriate size-extensivity correction to the MRCI(SD) correlation energies is developed which takes into account the open-shell character of the excited states. This approach is applicable to a wide range of polymers and crystals. In the present work trans-polyacetylene is chosen as a test system. The corresponding band structure is obtained with the correlation of all electrons in the system being included on a very high level of sophistication. The account of correlation effects leads to substantial shifts of the "center-of-mass" positions of the bands (valence bands are shifted upwards and conduction bands downwards) and a flattening of all bands compared to the corresponding HF band structure. The method reaches the quantum-chemical level of accuracy. Further an extention of the above approach to excitons (optical excitations) in crystals is developed which allows to use standard quantum-chemical methods to describe the electron-hole pairs and to finally obtain excitonic bands.