Exploring conformational landscapes of chiral molecules in their solvation and self-aggregation clusters

Our research program focuses on applying and developing new spectroscopic tools to bridge the gap of our understanding in terms of structural and dynamical properties of an isolated chiral molecule and of it in liquid phase and in solution. Using broadband rotational spectroscopy aided by high level ab initio calculations, we probe structural diversity and emerging bulk behavior in trimeric and tetrameric aggregates of the transiently chiral 2-fluoroethanol (FE). We show that the FE tetramer is an intriguing system at the interface between gas- and bulk-phase behavior, where the conformational specificity seen in the gas-phase is still experimentally relevant but plays a diminished role relative to the intermolecular topology and cooperative stability. In the second example, we examine conformational landscapes of tetrahydro-2-furoic acid (THFA), a chiral carboxylic acid, and its dimer and its complexes with water molecules in a jet expansion using rotational spectroscopy. We also apply vibrational circular dichroism and Raman optical activity to probe how intermolecular interactions with water and THFA itself influence the aforementioned conformational preference in condense phase directly. The interplay between experiment and theory is essential for all the work described.