TY - GEN UR - https://archiv.ub.uni-heidelberg.de/volltextserver/18764/ ID - heidok18764 Y1 - 2015/// TI - Top-down Modeling of Hierarchically Structured Soft Matter: Liquid Crystalline Mesophases of Polymeric Semiconductors A1 - Gemünden, Patrick AV - public N2 - This thesis addresses the development of generic, particle-based models for hierarchically structured polymeric soft matter, in which the macroscopic structure is linked to microscopic, molecular properties. The models are developed in a top-down approach, tailored to reproduce macroscopic properties of the real system, such as the general phase behavior. Methodologically, the models are derived from effective functionals (Hamiltonians) that depend on local scalar and tensorial order parameters, capturing liquid crystalline (LC) phases. The elastic properties of nematic LC polymer melts are studied. As one of the main results, a linear scaling of the splay Frank elastic constant with the chain length is found in the simulations, providing evidence for resolving a disagreement of existing theoretical predictions. Subsequently, a model is developed describing the large-scale morphology of polymeric semiconductors, as a test case for poly(3-hexylthiophene) (P3HT). The modeling of the lamellar, semi-crystalline morphology of real P3HT is, in a first step, developed for the less ordered LC phase. The non-bonded model interactions are soft and anisotropic, with additional biaxial symmetry capturing generically the anisotropy of the molecular architecture and the ?-stacking interactions. Macroscopic features of the real material, such as the dependence of the isotropic-nematic transition on the chain length, are reproduced. The morphologies are analyzed with respect to charge transport related properties. In the last part of the thesis, a multiscale scheme for the reconstruction of atomistic detail is presented. ER -