Experimental and theoretical studies in nuclear magnetic resonance

Abstract

Nuclear Magnetic Resonance (NMR) has proven to be an excellent tool to probe the structure of molecules by gaining insight into nuclear interactions. Used in conjunction with theoretical calculations, NMR has the potential to elucidate these nuclear interactions and how they affect structure, bonding and dynamics on a molecular scale. The first two projects presented herein study the peroxide explosive hexamethylene triperoxide diamine (HMTD). In the first project, we use the characteristics of the solid-state NMR lineshape to determine the 14N quadrupole coupling constant (C_Q). The second project uses multi-dimensional solution-state NMR and chiral shift reagents to show that there are two enantiomeric pairs of HMTD conformers. The third project introduces the new two-dimensional NMR technique Slow Turning Reveals Enormous Quadrupole Interactions (STREAQI) to find the nuclear electronic parameters in one experiment, when ordinarily the very large C _Q requires multiple experiments to obtain the entire lineshape. The final project studies the biological analog dimethylthiourea copper (I) chloride, in which the C_Q, chemical shift anisotropy (Δδ) and isotropic chemical shift (δ_i) are found using various experimental and theoretical methods.