Hydrogen bond, phonon assisted

SLR time results provide novel information on the temperature dependence and distribution of local RFs and their dynamics. A direct evidence for incoherent phonon-assisted deuteron tunnelling in H-bonded systems has been observed from NMR experiments. The use of quadrupole-perturbed ID 2H NMR spectroscopy and in particular 2D 2H NMR exchange spectroscopy has found to be very promising as regards elucidating the details of the hydrogen dynamics. 

Horsewill et al. (1994) examined the hydrostatic pressure effect on the proton transfer in crystals of a carboxylic acid dimer. Under a hydrostatic pressure, the distance of hydrogen bonds becomes shorter, and this is accompanied by a decrease in the potential barrier to proton transfer. The temperature dependence of the rate of the proton transfer turns out to be of a non-Arrhenius type. The influence of phonon-assisted tunnelling becomes evident as the external pressure increases, especially at lower temperatures. 

Fig. 9.12 Diagrammatic representations of the potential wells for the hydrogen atom in a H-bond as understood within the phonon assisted tunnelling model, shown above, and the independent proton model, below.

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