Bryce, David Lawson.2014-10-2120022002AAINQ75694http://hdl.handle.net/10222/55845To properly interpret the information available from nuclear magnetic resonance (NMR) parameters, it is advantageous to study the complete second-rank interaction tensors, i.e., chemical shift (CS), indirect nuclear spin-spin coupling (J), and electric field gradient (EFG) tensors. Two distinct courses of research based on a combined experimental and theoretical approach have been followed.Modern solid-state NMR techniques have been applied to several quadrupolar nuclei to characterize the magnitude and orientations of their EFG and CS tensors. Results have been obtained for 11B, 35/37Cl, 53Cr, and 95Mo at magnetic fields of 4.7 to 18.8 T. The first measurement of a boron CS tensor is reported and interpreted in terms of a simple MO picture. Chlorine NMR of organic hydrochlorides reveals a correlation between the chlorine EFG tensor and the local hydrogen bonding environment. The first 53Cr NMR spectra of diamagnetic solids are presented and analyzed. Mo-95 NMR results provide an example of the relationship between the local molecular and electronic structure and the molybdenum CS and EFG tensors. Ab initio and density-functional theory (DFT) calculations have been employed to complement the experimental data.The second aspect of the research involves the application of recent advances in the calculation of J via multiconfigurational SCF and relativistic DFT methods. Calculations on several diatomics for which highly precise experimental data exist from high-resolution molecular beam spectroscopy have helped to elucidate the connection between J and rotational hyperfine parameters. This connection has been exploited to establish the accuracy of the computational methods and to develop a more complete understanding of periodic trends in J coupling. This work illustrates the importance of various mechanisms which contribute to J. New insight into the phenomenon of J coupling between heavy nuclei across hydrogen bonds has been gained. The first experimental attempts to measure the antisymmetric part of J are reported.Thesis (Ph.D.)--Dalhousie University (Canada), 2002.Chemistry, Analytical.text