@phdthesis{Holch2009,
  author    = {Holch, Florian},
  title     = {Investigation of Intermolecular Interaction in Organic Thin Films by means of NEXAFS Spectroscopy},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-43630},
  school      = {Universit{\"a}t W{\"u}rzburg},
  year      = {2009},
  abstract  = {The present work reports on the electron-vibron coupling in large organic molecules and particularly on the intermolecular interaction in molecular condensates. The optical and electrical properties of these organic systems are in the focus of attention due to their crucial importance for the development of (hybrid) organic electronic devices. In particular, the charge transport mechanism and hence the interaction between condensed molecules is a matter of debate [1-4]. In order to shed light on this interaction, the spectroscopic signatures of isolated molecules in the gas phase and their condensed counterparts have been studied. The applied technique, near-edge x-ray absorption fine structure (NEXAFS) spectroscopy, is a local probe with high chemical selectivity, well suited for the investigation of the electronic structure of molecular valence levels [5]. In the experimental part, the experimental set-up developed in this work is described with special attention to the characteristic issues of gas phase measurements, energy calibration and the subsequent data evaluation. The high quality gas phase and solid state NEXAFS spectra are analysed with respect to energy positions, shape and intensity of the sharp pi*-resonances characteristic for these aromatic molecules. Where applicable, a detailed Franck-Condon (FC) analysis of the vibronic fine structure has been performed, yielding additional information on the changes that occur upon solid state formation. Together with former results on vibrational features in large organic molecules, this information has been used to investigate the correlation of vibrational energies in the ground and electronically excited state. We find a relatively good agreement with other empirical studies on vibronic structures in photoelectron spectroscopy (PES) spectra of small molecules [6]. The molecular compounds investigated are in general believed to interact via weak van-der-Waals forces only. The present results however reveal distinct differences between the spectra of the gas and solid phase that can not be explained within the context of a mere interaction by dispersive forces. In detail, differential red-shifts of 0.1 to 0.3eV of transitions assigned to the aromatic system have been observed in the C-K spectra of benzene-tetracarboxylic acid dianhydride (BTCDA), 1,4,5,8-naphthalene-tetracarboxylic acid dianhydride (NTCDA), and 3,4,9,10-perylene-tetracarboxylic acid dianhydride (PTCDA) upon solid state formation. From BTCDA to PTCDA the shift increases, indicating an improving intermolecular interaction with molecular size or a closer molecular packing. In contrast, all transitions assigned to the anhydride carbon atom (C1) do not show any shift. For the O-K spectra, small changes in relative intensity have been observed for BTCDA and NTCDA. In case of PTCDA, a blue-shift of up to 0.2eV is evident for the OB 1sLEMO+1 transition. Theoretical models for the intermolecular interaction have been proposed in this work, based on a change of molecular geometry and interaction of adjacent molecules in the ground and excited state, respectively. While an interaction of adjacent molecular orbitals may explain the experimental findings for one particular molecule, this model falls short for a comprehensive explanation of all three dianhydrides. For an interaction in the excited state, the excitonic coupling with the neighbours attached at an angle, quantum chemical calculations yield no significant change in peak positions for NTCDA. Unfortunately, results for the stacked neighbours as well as the larger compound PTCDA are still lacking. For tris (8-quinolinol) aluminum (Alq3), the observed peak-shifts are restricted to just one unoccupied orbital, the LEMO+2, which is mainly localised at the phenoxide side of the quinolinol ligands. Although the shifts differ for the individual edges, the main interaction can therefore be assigned to this orbital. In summary, NEXAFS spectroscopy, if performed with great care in terms of experimental details and data analysis especially for the gas phase data, provides very detailed and highly interesting data on the changes of the electronic structure of organic molecules upon condensation. The present data can be applied as a reference for further experimental and (highly desired) theoretical investigations, which are needed for a comprehensive understanding of the complex interaction mechanisms between organic molecules.},
  subject      = {Organisches Molek{\"u}l},
  language  = {en}
}
@phdthesis{Noller2009,
  author    = {Noller, Bastian},
  title     = {Excited-State Dynamics of Organic Intermediates},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-36075},
  school      = {Universit{\"a}t W{\"u}rzburg},
  year      = {2009},
  abstract  = {This thesis gives insights into the real-time dynamics of several free carbenes and radicals on a femtosecond and nanosecond time scale. The experiments were performed with radicals, singlet carbenes and triplet carbenes of various sizes. Several neutral excited states as well as the ionic ground state were characterized. Despite the relevance of such reactive intermediates in almost all chemical reactions, only relatively little experimental information on such systems is found in the literature. This is linked to the experimental challenge of producing such species under isolated conditions. The intermediates are formed from precursor molecules under interaction- free conditions by supersonic jet flash pyrolysis. The precursor molecules were synthetically designed to show clean thermal dissociation into one specific intermediate. A large variety of spectroscopic techniques was applied to study the intermediates. Each method augments the results of the other methods. This enabled to successfully approach the main goal of this thesis: to understand the excited-state dynamics of organic intermediates. The excited states were found to deactivate rapidly to the hot ground state. The observed fast decay is presumably linked to coupled electronically excited states and relaxation takes place by internal conversion or conical intersections. Further reactions then take place on the ground state surface. Absorption spectra, photodissociation dynamics, photoelectron spectra, ionization potentials, excited-state lifetimes and dissociative photoionization were elucidated by the measurements. Pulsed and continuous light sources were used over a large spectral range (UV, Vis, VUV). A well-defined amount of energy was deposited into the molecule. After internal conversion has taken place, a microcanonical ensemble of reactive intermediates can be studied. This data helps to understand the energetics and reaction channels of intermediates. Velocity map imaging enabled to monitor the pyrolysis efficiency in real time by analyzing photoion images. This observation facilitates clean intermediate generation. Experimental results were compared to quantum chemical calculations to aid the interpretation as well as to test the performance of theoretical approaches. Hydrocarbon radicals and carbenes are regarded as benchmark systems for computational methods due to their several low-lying electronic states and open-shell electronic configuration. The experimental data can help to identify and understand the contributions of the examined intermediates to the chemistry of high energy environments (e. g., hydrocarbon cracking reactors, interstellar space and combustion chambers). Here increased numbers of hydrocarbon intermediates are often present and usually have a strong impact on the overall reaction mechanism. Such environments contain in general a complex mixture of several different intermediates. The more spectroscopic and dynamic properties of each isolated intermediate are known, the easier it is to identify it among multiple components and to understand how it contributes to the overall reaction mechanism. Electronic excitation can take place by radiation, particle collisions or thermally at very high temperatures. How excited states influence the reaction mechanisms is still a matter of currant research.},
  subject      = {Excited-State Dynamics of Organic Intermediates},
  language  = {en}
}