Electronic-structure interactions in aqueous solutions: a liquid-jet photoelectron-spectroscopy study

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This thesis discusses advancements in electronic-structure measurements through the development of the vacuum liquid-microjet technique for photoelectron spectroscopy. The focus is on transition-metal aqueous solutions and DNA components in water, which are central to current research in physical chemistry and biology, particularly regarding molecular interactions with water. For metal solutions, both direct and resonant photoelectron spectroscopy are employed to determine absolute binding energies and reorganization energies of redox pairs in water. The research reveals detailed information on electronic relaxation processes of core-excited metal ions and solvent molecules, with the nature of relaxation reflecting the structure of the transition-metal-water complex and ultrafast charge transfers. Insights into complex multi-electron interactions in aqueous environments are particularly significant for transition metal ions with incomplete 3d valence levels. Selected results from various transition-metal solutions are presented. Additionally, studies on biologically relevant molecules focus on the valence energies of nucleotide building blocks, examining how the lowest ionization energy of nucleobases in water changes with the addition of sugar and phosphate, and comparing bulk solvation with micro-hydration. Initial resonant photoelectron studies on these systems are also described, highlighting electronic coupling between ni