Ab Initio Methods for Chiroptical Properties of Molecules in Solution

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T. Daniel Crawford of Virginia Polytechnic Institute and State University is supported by the Chemical Theory, Models and Computational Methods Program in Chemistry and the Office of Cyberinfrastructure to develop methods that provide accurate predictions of the optical properties of chiral molecules in solution. The methods are based on coupled cluster linear response theory extended to incorporate solvent perturbations via both explicit and implicit models. This approach is systematically testable and convergent, benefitting from reduced-scaling implementations under development in the Crawford group that allow calculations involving many dozens of atoms. Applications include calculations of solution-phase optical rotation and circular dichroism spectra, and direct comparison with experiment. Results of this research include new chemical models that are embodied in sustainable software made freely available through the open-source PSI program package. The research provides valuable insight into the assignment of the absolute stereochemistry of natural products, as well as into the fundamental connections between molecular structure and the optical properties of chiral molecules. Educational efforts are directed towards training the next generation of computational scientists and the continued development of undergraduate computational laboratory experiments.