@phdthesis{Hantschmann2023,
  author    = {Hantschmann, Markus},
  title     = {Stimulated resonant inelastic X-ray scattering in transition metal systems},
  doi       = {10.25932/publishup-58476},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-584761},
  school      = {Universit{\"a}t Potsdam},
  pages     = {xv, 160},
  year      = {2023},
  abstract  = {With the implementation of intense, short pulsed light sources throughout the last years, the powerful technique of resonant inelastic X-ray scattering (RIXS) became feasible for a wide range of experiments within femtosecond dynamics in correlated materials and molecules. In this thesis I investigate the potential to bring RIXS into the fluence regime of nonlinear X-ray-matter interactions, especially focusing on the impact of stimulated scattering on RIXS in transition metal systems in a transmission spectroscopy geometry around transition metal L-edges. After presenting the RIXS toolbox and the capabilities of free electron laser light sources for ultrafast intense X-ray experiments, the thesis explores an experiment designed to understand the impact of stimulated scattering on diffraction and direct beam transmission spectroscopy on a CoPd multilayer system. The experiments require short X-ray pulses that can only be generated at free electron lasers (FEL). Here the pulses are not only short, but also very intense, which opens the door to nonlinear X-ray-matter interactions. In the second part of this thesis, we investigate observations in the nonlinear interaction regime, look at potential difficulties for classic spectroscopy and investigate possibilities to enhance the RIXS through stimulated scattering. Here, a study on stimulated RIXS is presented, where we investigate the light field intensity dependent CoPd demagnetization in transmission as well as scattering geometry. Thereby we show the first direct observation of stimulated RIXS as well as light field induced nonlinear effects, namely the breakdown of scattering intensity and the increase in sample transmittance. The topic is of ongoing interest and will just increase in relevance as more free electron lasers are planned and the number of experiments at such light sources will continue to increase in the near future. Finally we present a discussion on the accessibility of small DOS shifts in the absorption-band of transition metal complexes through stimulated resonant X-ray scattering. As these shifts occur for example in surface states this finding could expand the experimental selectivity of NEXAFS and RIXS to the detectability of surface states. We show how stimulation can indeed enhance the visibility of DOS shifts through the detection of stimulated spectral shifts and enhancements in this theoretical study. We also forecast the observation of stimulated enhancements in resonant excitation experiments at FEL sources in systems with a high density of states just below the Fermi edge and in systems with an occupied to unoccupied DOS ratio in the valence band above 1.},
  language  = {en}
}
@phdthesis{Buechner2022,
  author    = {B{\"u}chner, Robby},
  title     = {Understanding local electronic structure variations in bio-inspired aromatic molecules},
  doi       = {10.25932/publishup-55319},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-553192},
  school      = {Universit{\"a}t Potsdam},
  pages     = {viii, 111},
  year      = {2022},
  abstract  = {In this thesis, the dependencies of charge localization and itinerance in two classes of aromatic molecules are accessed: pyridones and porphyrins. The focus lies on the effects of isomerism, complexation, solvation, and optical excitation, which are concomitant with different crucial biological applications of specific members of these groups of compounds. Several porphyrins play key roles in the metabolism of plants and animals. The nucleobases, which store the genetic information in the DNA and RNA are pyridone derivatives. Additionally, a number of vitamins are based on these two groups of substances. This thesis aims to answer the question of how the electronic structure of these classes of molecules is modified, enabling the versatile natural functionality. The resulting insights into the effect of constitutional and external factors are expected to facilitate the design of new processes for medicine, light-harvesting, catalysis, and environmental remediation. The common denominator of pyridones and porphyrins is their aromatic character. As aromaticity was an early-on topic in chemical physics, the overview of relevant theoretical models in this work also mirrors the development of this scientific field in the 20th century. The spectroscopic investigation of these compounds has long been centered on their global, optical transition between frontier orbitals. The utilization and advancement of X-ray spectroscopic methods characterizing the local electronic structure of molecular samples form the core of this thesis. The element selectivity of the near-edge X-ray absorption fine structure (NEXAFS) is employed to probe the unoccupied density of states at the nitrogen site, which is key for the chemical reactivity of pyridones and porphyrins. The results contribute to the growing database of NEXAFS features and their interpretation, e.g., by advancing the debate on the porphyrin N K-edge through systematic experimental and theoretical arguments. Further, a state-of-the-art laser pump - NEXAFS probe scheme is used to characterize the relaxation pathway of a photoexcited porphyrin on the atomic level. Resonant inelastic X-ray scattering (RIXS) provides complementary results by accessing the highest occupied valence levels including symmetry information. It is shown that RIXS is an effective experimental tool to gain detailed information on charge densities of individual species in tautomeric mixtures. Additionally, the hRIXS and METRIXS high-resolution RIXS spectrometers, which have been in part commissioned in the course of this thesis, will gain access to the ultra-fast and thermal chemistry of pyridones, porphyrins, and many other compounds. With respect to both classes of bio-inspired aromatic molecules, this thesis establishes that even though pyridones and porphyrins differ largely by their optical absorption bands and hydrogen bonding abilities, they all share a global stabilization of local constitutional changes and relevant external perturbation. It is because of this wide-ranging response that pyridones and porphyrins can be applied in a manifold of biological and technical processes.},
  language  = {en}
}