Abstract

Nuclear spin-induced optical rotation (NSOR) is a nuclear magneto-optic effect manifesting as a rotation of the plane of polarization of linearly polarized light induced by nuclear magnetic moments within a molecule. NSOR probes molecular optical properties through localized nuclear interactions and has potential to be developed into a new spectroscopic tool. However, so far the connection between the molecular structure and NSOR response has not been systematically investigated. To obtain insight into this relation and to assess its viability as a foundation for a new spectroscopic method, NSOR of ¹H and ¹³C nuclei in a set of hydrocarbon molecules with various structural motifs is theoretically investigated using density functional theory calculations. The results reveal that NSOR intensities are correlated with several structural features of the molecules, such as the position of the nucleus in the carbon chain, isomerism and presence of nearby unsaturated groups. Specific patterns connecting NSOR to the local chemical environment of the nucleus can be observed. It is also shown that this effect can be to a good approximation modelled as a sum of individual contributions from nearby chemical groups, allowing for a rapid estimation of its values. The demonstrated systematic dependence of the NSOR signal on the molecular structure is a desirable feature for theoretical and experimental development of new spectroscopic methods based on this phenomenon.