Tunnelling magnetic resonances: Dynamic nuclear polarisation and the diffusion of methyl group tunnelling energy
The dynamic nuclear polarisation (DNP) of (1)H spins arising from methyl tunnelling magnetic resonances has been investigated in copper-doped zinc acetate dihydrate using field-cycling NMR spectroscopy at 4.2K. The tunnel resonances appear in the field range 20-50 mT and trace out the envelope of the electron spin resonance spectrum of the Cu(2+) ion impurities. By investigating the DNP line shapes as a function of time, the cooling of the methyl tunnel reservoir has been probed. The role of spectral diffusion of tunnelling energy in determining the DNP line shapes has been investigated through experiments and numerical simulations based on a theoretical model that describes the time evolution of the (1)H polarisation and the tunnelling temperature. The model is discussed in detail in comparison with the experiments. All effects have been studied as a function of Cu(2+) ion concentration.
- [Show abstract] [Hide abstract] ABSTRACT: Using low temperature dynamic nuclear polarisation (DNP) in conjunction with dissolution makes it possible to generate highly polarised nuclear spin systems for liquid state applications of nuclear magnetic resonance spectroscopy. However, in its current implementation, which requires the transfer of the solute between two different magnets, the hyperpolarisation strategy is limited to spin systems with relatively long longitudinal relaxation time constants. Here we describe the design and construction of a dedicated spectrometer for DNP applications that is based on a magnet with two isocentres. DNP enhancement is carried out in the upper compartment of this magnet in a low temperature environment at 3.35 T, while a 9.4 T isocentre in the lower compartment is used for high resolution NMR spectroscopy. The close proximity (85 cm) of the two isocentres makes it possible to transfer the sample in the solid state with very little loss of spin polarisation. In first performance tests this novel experimental set-up proved to be superior to the strategy involving two separate magnets.0Comments 52Citations
- [Show abstract] [Hide abstract] ABSTRACT: Long-lived nuclear spin states have a relaxation time much longer than the longitudinal relaxation time T 1. Long-lived states extend significantly the time scales that may be probed with magnetic resonance, with possible applications to transport and binding studies, and to hyperpolarised imaging. Rapidly rotating methyl groups in solution may support a long-lived state, consisting of a population imbalance between states of different spin exchange symmetries. Here, we expand the formalism for describing the behaviour of long-lived nuclear spin states in methyl groups, with special attention to the hyperpolarisation effects observed in 13CH3 groups upon rapidly converting a material with low-barrier methyl rotation from the cryogenic solid state to a room-temperature solution [M. Icker and S. Berger, J. Magn. Reson. 219, 1 (2012)]. We analyse the relaxation properties of methyl long-lived states using semi-classical relaxation theory. Numerical simulations are supplemented with a spherical-tensor analysis, which captures the essential properties of methyl long-lived states.0Comments 13Citations
- [Show abstract] [Hide abstract] ABSTRACT: 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.0Comments 1Citation