@PhdThesis{diss_mods_00023207, author = {Raeker, Tim}, title = {Full-Dimensional Photodynamics Simulations:From Photoisomerizations to Excited-State Proton Transfer Reactions}, year = {2018}, publisher = {Christian-Albrechts-Universit{\"a}t zu Kiel}, address = {Kiel}, keywords = {photodynamics; computer chemistry; proton transfer; switching; photoisomerization; azobenzene; Photodynamik; Computerchemie; Protontransfer; Schalten; Photoisomerisierung; Azobenzol}, abstract = {Photoactive molecules are studied for their electronic properties and are also being designed for use in specific applications or even molecular machines. Two photochemical reactions are investigated in this thesis: trans<->cis photoisomerization (``switching'') and excited-state intramolecular proton transfer (ESIPT). The first reaction type is represented by the newest generation of bridged-azobenzene derivatives, indandiazocine and diindandiazocine which were designed to achieve chiral trans{\textrightarrow}cis isomerization as an upgrade over their parent system diazocine. This predicted feature is validated by calculations of the actual photodynamics of these systems. In a second project, azobenzene and the three aforementioned bridged azobenzenes are used as motors in an artificial cilium that served as a prototype for a molecular particle transport machine. Full-dimensional calculations of the ESIPT dynamics of salicylic acid and several other derivatives are presented for the first time here, all featuring a so-called "crane-switching" motif. With 7-hydroxy-4-methylquinoline-8-carbaldehyde (HMQCA) a more complex ESIPT system is also investigated which utilizes the crane-switching to allow for a PT to a different site of the molecule than the initial proton donor. The computational model of choice for calculating the photodynamics is semiempirical quantum mechanics (SEQM) coupled to floating-occupation configuration interaction. SEQM relies on parameters that are fitted to reproduce a set of molecular properties. However, the studied ESIPT systems -- or excited-state properties in general -- are not part of such a set. Hence, deficiencies were encountered when comparing the obtained results to the results of ab initio QM methods.}, url = {https://macau.uni-kiel.de/receive/diss_mods_00023207}, file = {:https://macau.uni-kiel.de/servlets/MCRFileNodeServlet/dissertation_derivate_00007736/thesis_raeker.pdf:PDF}, language = {en} }