@phdthesis{Scholz2013,
  author    = {Scholz, Markus},
  title     = {Energy-Dispersive NEXAFS: A Novel Tool for the Investigation of Intermolecular Interaction and Structural Phase Dynamics},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-83839},
  school      = {Universit{\"a}t W{\"u}rzburg},
  year      = {2013},
  abstract  = {In the context of this thesis, the novel method soft X-ray energy-dispersive NEXAFS spectroscopy was explored and utilized to investigate intermolecular coupling and post-growth processes with a temporal resolution of seconds. 1,4,5,8- naphthalene tetracarboxylic acid dianhydride (NTCDA)multilayer films were the chosen model system for these investigations. The core hole-electron correlation in coherently coupled molecules was studied by means of energy-dispersive near-edge X-ray absorption fine-structure spectroscopy. A transient phase was found which exists during the transition between a disordered condensed phase and the bulk structure. This phase is characterized by distinct changes in the spectral line shape and energetic position of the X-ray absorption signal at the C K-edge. The findings were explained with the help of theoretical models based on the coupling of transition dipole moments, which are well established for optically excited systems. In consequence, the experimental results provides evidence for a core hole-electron pair delocalized over several molecules. Furthermore, the structure formation of NTCDA multilayer films on Ag(111) surfaces was investigated. With time-resolved and energy-dispersive NEXAFS experiments the intensity evolution in s- and p-polarization showed a very characteristic behavior. By combining these findings with the results of time-dependent photoemission measurements, several sub-processes were identified in the post- growth behavior. Upon annealing, the amorphous but preferentially flat-lying molecules flip into an upright orientation. After that follows a phase characterized by strong intermolecular coupling. Finally, three-dimensional islands are established. Employing the Kolmogorov-Johnson-Mehl-Avrami model, the activation energies of the sub-processes were determined.},
  subject      = {Organisches Molek{\"u}l},
  language  = {en}
}
@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}
}