Vibrational Raman optical activity (ROA) is one available approach to the determination of absolute molecular stereochemistry. Such assignments require confidence in the ability of theory to predict the sign and magnitudes of the chiroptical responses in advance. In 2011, Crawford and Ruud presented the first theoretical ROA spectra obtained using coupled-cluster theory, opening the possibility of rigorous testing of more approximate and widely used methods. Although challenges to agreement with experiment abound (including the effects of anharmonicity, solvation, and multiplicity of molecular conformations), extensive experience with optical rotation suggests that the accuracy of even the fundamental electronic structure itself should not be too readily assumed. Furthermore, a peculiarity of vibrational ROA is the variety of different inputs (e.g., geometry, force field and normal modes, property tensors) that contribute to the predicted spectra. The results of extensive testing will highlight the relative importance of these factors in the computation of coupled-cluster ROA spectra, and the quality of agreement with those computed with density functional theory.

Coupled-cluster theory investigations of vibrational Raman optical activity

2019 Fall National Meeting

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