NMR Spin-Lattice Relaxation and Tunnelling of Partially Deuterated Methyl Groups

Abstract
Proton spin lattice relaxation rates have been measured at 15 and 30 MHz and down to 5 K for the partially deuterated molecular crystals 4-F-toluene, 4-Cl-toluene, and 2,6-Cl2-toluene. The behaviour of these materials is governed by methyl group tunnelling. As compared with the undeuterated compounds, the low temperature relaxation is enhanced and the details depend on the removal of the symmetry coupling between rotator and spin states. The hindering barriers remain unchanged, the A to E conversion rates are faster, and relaxation is dominated by spectral density contributions J(2ωo) and J(2ω0). In one case an additional influence of level-crossing energy transfer on relaxation is observed. Field-cycling spectroscopy reveals steps rather than peaks if the proton spin Zeeman and tunnelling splittings match

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