This dissertation examines five different molecules with respect to their geometries in the ground and excited states and their dynamics after electronic excitation. The focus is on pi-conjugated systems, bridged (paracyclophane derivatives) or Extended (pyracen) by an additional aliphatic moiety. Paracyclophanes are suitable models to study the interaction between pi-systems, in particular the through space coupling. Moreover, this work focuses on the excited-state dynamics of the B-state of 2-methylallyl (2MA) by time-resolved photoionization with a ps-laser. Research on resonantly stabilized small radicals such as allyl or methylallyl is not only conducted because of a fundamental interest in reaction dynamics, but also because such radicals can accumulate in a reactive environment and are observed in combustion. Studies on isolated radicals yield information on their reactions, which are important in kinetic modeling of combustion processes. For example, biodiesel often contains molecules with C=C double bonds (e.g. fatty acid esters). Abstraction of H-atoms leads to alkylated allyl radicals, because the C-H bonds at the allylic sites are particularly weak. Due to their instability, such small hydrocarbon radicals are not easy to handle and their spectroscopic measurement is always a challenge. An innovation in my research was the development of a high-temperature gas cell to transfer the molecules into the gas phase and to record IR-spectra (compatible with an FT-IR spectrometer), obtaining experimental information on the most stable conformer in the electronic ground state.
|Advisor:||Fischer , Ingo|
|School:||Bayerische Julius-Maximilians-Universitaet Wuerzburg (Germany)|
|Source:||DAI-C 81/7(E), Dissertation Abstracts International|
Copyright in each Dissertation and Thesis is retained by the author. All Rights Reserved
The supplemental file or files you are about to download were provided to ProQuest by the author as part of a
dissertation or thesis. The supplemental files are provided "AS IS" without warranty. ProQuest is not responsible for the
content, format or impact on the supplemental file(s) on our system. in some cases, the file type may be unknown or
may be a .exe file. We recommend caution as you open such files.
Copyright of the original materials contained in the supplemental file is retained by the author and your access to the
supplemental files is subject to the ProQuest Terms and Conditions of use.
Depending on the size of the file(s) you are downloading, the system may take some time to download them. Please be