Intra- and intermolecular dispersion forces: Understanding complex formation, aggregation, and the effect of solvation using a bottom-up approach

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The goal of the research program is to significantly advance the current understanding of the role of dispersion interaction in molecular recognition and intramolecular structures by systematically exploring model systems using high-resolution rotational spectroscopy. We will continue our successful work on spectroscopically investigating and characterizing molecular systems in the gas phase to understand and quantify intra- and intermolecular interactions. In a bottom-up approach, we will study basic processes relevant for understanding molecular aggregation and finally the transition from the gas to the bulk phase, as well as the influence of solvation on dispersion. For the second funding period, we can now build on a solid, fruitful, and creative network of synthesis, spectroscopy, and theoretical chemistry groups, as described above. We propose to work on the following aspects:In project 1, it is our goal to further investigate qualitatively and quantitatively the role of dispersion for a variety of molecular complexes. We will continue our work on ether-alcohol complexes (which already let to a number of surprises in the first funding period) and extend it to ketone-alcohol complexes as well as chiral species, in collaboration with our partner groups. We aim at gaining a complete understanding of how dispersion contributions influence the structures of complexes and which role conformational flexibility plays.In a second project, we will study aggregation of molecules, such as those with extended π systems, and we will thus explore the transition from individual molecules to the bulk on the molecular level. The anticipated results on a molecule-by-molecule build-up mechanism will also be of interest for the formation of soot particles as relevant for combustion as well as of dust grains as relevant for astrochemistry.In project 3, we will investigate how dispersion is influenced by solvation. We will study molecular complexes, such as diphenylether-methanol, and investigate how structural preferences upon clusters formation are modulated by stepwise solvation of the complex. The controlled conditions in a molecular jet are ideally suited for such experiments. We aim at understanding how the effect of solvation depends on the different molecule systems, and how this can be predicted and finally controlled.