Computational investigations of nuclear magnetic resonance and magneto-optic properties at the basis-set limit

Theoretical examination of traditional nuclear magnetic resonance (NMR) parameters as well as novel quantities related to magneto-optic phenomena is carried out in this thesis for a collection of organic molecules. Electronic structure methods are employed, and reliable calculations involving large molecules and computationally demanding properties are made feasible through the use of completeness-optimized basis sets. In addition to introducing the foundations of NMR, a theory for the nuclear spininduced optical rotation (NSOR) is formulated. In the NSOR, the plane of polarization of linearly polarized light is rotated by spin-polarized nuclei in an NMR sample as predicted by the Faraday effect. It has been hypothesized that this could be an advantageous alternative to traditional NMR detection. The opposite phenomenon, i.e., the laser-induced NMR splitting, is also investigated. Computational methods are discussed, including the method of completeness optimization. Nuclear shielding and spin-spin coupling are evaluated for hydrocarbon systems that simulate graphene nanoflakes, while the laser-induced NMR splitting is studied for hydrocarbons of increasing size in order to find molecules that may potentially interest the experimentalist. The NSOR is calculated for small organic systems with inequivalent nuclei to prove the existence of an optical chemical shift. The existence of the optical shift is verified in a combined experimental and computational study. Finally, relativistic effects on the size of the optical rotation are evaluated for xenon, and they are found to be significant. Completeness-optimized basis sets are used in all cases, and extensive analysis regarding the accuracy of results is made.