Quantum dynamics and tunnelling of methyl rotors studied by field-cycling NMR

Sun, Cheng (2009) Quantum dynamics and tunnelling of methyl rotors studied by field-cycling NMR. PhD thesis, University of Nottingham.

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Abstract

Quantum dynamics and tunnelling of methyl rotors has been studied using field-cycling nuclear magnetic resonance (NMR) spectrometer, in a variety of samples. The characteristic frequency of the tunnelling motion of methyl groups has been investigated using both low-field dipole-dipole driven experiments and tunnel resonance level-crossing experiments. The classical hopping and quantum tunnelling of methyl groups have been studied by making temperature-dependent and field-dependent measurements of the spin-lattice relaxation time T1. The spectral density functions of the dipolar interaction, mediated by the rotation of methyl groups, have been directly plotted, and the correlation times characteristic of the rotational motion have been determined.

Electron spin resonance (ESR) tunnel resonance spectra have been studied in samples with unpaired electrons by making resonant contact between the methyl tunnelling reservoir and the electron spins. The phenomenon of dynamic proton polarisation (DNP) has also been investigated in these samples. Experiments demonstrating the cooling of methyl tunnelling reservoir and the diffusion of energy amongst tunnelling reservoirs are presented.

In low-field dipole-dipole driven experiments, in order to avoid the tunnelling transition saturation problem, the sideband stirring radiofrequency (rf) irradiation technique has been utilised and the low-field NMR spectra have been observed with enhanced sideband peaks. The rf irradiation time-dependence of the low-field spectra has been investigated.

The experimental data is supported by numerical simulations, using appropriate theoretical models.

Item Type:Thesis (PhD)
Supervisors:Horsewill, Anthony J.
Owers-Bradley, John R.
Uncontrolled Keywords:solid-state, NMR, field-cycling NMR, quantum dynamics, quantum tunnelling, low temperature, mehtyl
Faculties/Schools:UK Campuses > Faculty of Science > School of Physics and Astronomy
ID Code:751
Deposited By:Mr Cheng Sun
Deposited On:09 Dec 2009 12:01
Last Modified:09 Dec 2009 12:01

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