Spin-symmetry conversion in methyl rotors induced by tunnel resonance at low temperature.

Field-cycling NMR in the solid state at low temperature (4.2 K) has been employed to measure the tunneling spectra of methyl (CH3) rotors in phenylacetone and toluene. The phenomenon of tunnel resonance reveals anomalies in (1)H magnetization from which the following tunnel frequencies have been determined: phenylacetone, νt = 6.58 ± 0.08 MHz; toluene, νt(1) = 6.45 ± 0.06 GHz and νt(2) = 7.07 ± 0.06 GHz. The tunnel frequencies in the two samples differ by three orders of magnitude, meaning different experimental approaches are required. In phenylacetone the magnetization anomalies are observed when the tunnel frequency matches one or two times the (1)H Larmor frequency. In toluene, doping with free radicals enables magnetization anomalies to be observed when the tunnel frequency is equal to the electron spin Larmor frequency. Cross-polarization processes between the tunneling and Zeeman systems are proposed and form the basis of a thermodynamic model to simulate the tunnel resonance spectra. These invoke space-spin interactions to drive the changes in nuclear spin-symmetry. The tunnel resonance lineshapes are explained, showing good quantitative agreement between experiment and simulations.

1H-19F spin-lattice relaxation spectroscopy: proton tunnelling in the hydrogen bond studied by field-cycling NMR.

Proton tunnelling in the hydrogen bonds of two fluorine substituted benzoic acid dimers has been investigated using field-cycling NMR relaxometry. The close proximity of the (19)F nuclei to the hydrogen bond protons introduces heteronuclear (19)F-(1)H dipolar interactions into the spin-lattice relaxation processes. This renders the (1)H magnetisation-recovery biexponential and introduces multiple spectral density components into the relaxation matrix characterised by frequencies that are sums and differences of the (19)F and (1)H Larmor frequencies. Using field-cycling NMR pulse sequences that measure the spin-lattice relaxation and cross-relaxation rates we demonstrate how some of these multiple spectral density components can be separately resolved. This leads to an accurate determination of the correlation times that characterise the proton tunnelling motion. A broad spectrum of relaxation behaviour is illustrated and explored in the chosen samples and the investigation is used to explore the theory and practise of field-cycling NMR relaxometry in cases where heteronuclear interactions are significant.