| dc.description.abstract | Chiroptical spectroscopy relies on the differential interaction of left- and right-circularly polarized light with chiral molecules. Chiral molecules are ubiquitous in nature and chemistry, and thus the elucidation of their overall three-dimensional structure, or Absolute Configuration (AC), is of fundamental importance to the pharmaceutical industry and chemists alike. Electronic Circular Dichroism (ECD) spectroscopy and its vibrational counterparts, Vibrational Circular Dichroism (VCD) and Vibrational Raman Optical Activity (VROA), can be combined with molecular modeling to determine the AC of chiral molecules. In cases of exotic chirality, such as isotopic chirality or mechanical chirality, chiroptical spectroscopies provide an effective means of probing the three-dimensional chirality and studying these systems. VCD and VROA are sensitive to the distribution of low-energy conformers as well as hydrogen bonding effects in solution. Additionally, VCD is especially sensitive to the formation of dimers or higher-order aggregates. The elucidation of the structures of these complexes remains a critical challenge in chiroptical spectroscopy due to the computational costs and difficulties associated with modeling these complexes and efficiently sampling their conformational spaces. This work focused on molecules possessing exotic chirality, conformational mobility, and the formation of strong intermolecular interactions. Each of these pose a significant challenge to the practical utility of chiroptical spectroscopy. | |
