Theoretical and Experimental Studies in Nuclear Magnetic Resonance

Nuclear magnetic resonance (NMR) is a tool used to probe the physical and chemical environments of specific atoms in molecules. This research explored small molecule analogues to biological materials to determine NMR parameters using ab initio computations, comparing the results with solid-state NMR measurements. Models, such as dimethyl phosphate (DMP) for oligonucleotides or CuCl for the active site of the protein azurin, represented computationally unwieldy macromolecules. 31P chemical shielding tensors were calculated for DMP as a function of torsion angles, as well as for the phosphate salts, ammonium dihydrogen phosphate (ADHP), diammonium hydrogen phosphate, and magnesium dihydrogen phosphate. The computational DMP work indicated a problem with the current standard 31P reference of 85% H3PO4(aq.). Comparison of the calculations and experimental spectra for the phosphate salts indicated ADHP might be a preferable alternative as a solid state NMR reference for 31P. Experimental work included magic angle spinning experiments on powder samples using the UNL chemistry department’s Bruker Avance 600 MHz NMR to collect data to determine chemical shielding anisotropies. For the quadrupolar nuclei of copper and scandium, the electric field gradient was calculated in diatomic univalent metal halides, allowing determination of the minimal level of theory necessary to compute NMR parameters for these nuclei.

Robust isothermal electric control of exchange bias at room temperature

Voltage-controlled spin electronics is crucial for continued progress in information technology. It aims at reduced power consumption, increased integration density and enhanced functionality where non-volatile memory is combined with highspeed logical processing. Promising spintronic device concepts use the electric control of interface and surface magnetization. From the combination of magnetometry, spin-polarized photoemission spectroscopy, symmetry arguments and first-principles calculations, we show that the (0001) surface of magnetoelectric Cr2O3 has a roughness-insensitive, electrically switchable magnetization. Using a ferromagnetic Pd/Co multilayer deposited on the (0001) surface of a Cr2O3 single crystal, we achieve reversible, room-temperature isothermal switching of the exchange-bias field between positive and negative values by reversing the electric field while maintaining a permanent magnetic field. This effect reflects the switching of the bulk antiferromagnetic domain state and the interface magnetization coupled to it. The switchable exchange bias sets in exactly at the bulk Néel temperature.