Rotating-frame nuclear magnetic relaxation of spins diffusing on a disordered lattice: a Monte Carlo model

The rotating-frame nuclear magnetic relaxation rate of spins diffusing on a disordered lattice has been calculated by Monte Carlo methods. The disorder includes not only variation in the distances between neighbouring spin sites but also variation in the hopping rate associated with each site. The presence of the disorder, particularly the hopping rate disorder, causes changes in the time-dependent spin correlation functions which translate into asymmetry in the characteristic peak in the temperature dependence of the dipolar relaxation rate. The results may be used to deduce the average hopping rate from the relaxation but the effect is not sufficiently marked to enable the distribution of the hopping rates to be evaluated. The distribution, which is a measure of the degree of disorder, is the more interesting feature and it has been possible to show from the calculation that measurements of the relaxation rate as a function of the strength of the radiofrequency spin-locking magnetic field can lead to an evaluation of its width. Some experimental data on an amorphous metal - hydrogen alloy are reported which demonstrate the feasibility of this novel approach to rotating-frame relaxation in disordered materials.

The role of space charge formation in the generation of thermally stimulated current (TSC) spectroscopy data for a model amorphous drug system

Thermally stimulated current (TSC) spectroscopy is attracting increasing attention as a means of materials characterization, particularly in terms of measuring slow relaxation processes in solid samples. However, wider use of the technique within the pharmaceutical field has been inhibited by difficulties associated with the interpretation of TSC data, particularly in terms of deconvoluting dipolar relaxation processes from charge distribution phenomena. Here, we present evidence that space charge and electrode contact effects may play a significant role in the generation of peaks that have thus far proved difficult to interpret. We also introduce the use of a stabilization temperature in order to control the space charge magnitude. We have studied amorphous indometacin as a model drug compound and have varied the measurement parameters (stabilization and polarization temperatures), interpreting the changes in spectral composition in terms of charge redistribution processes. More specifically, we suggested that charge drift and diffusion processes, charge injection from the electrodes and high activation energy charge redistribution processes may all contribute to the appearance of shoulders and 'spurious' peaks. We present recommendations for eliminating or reducing these effects that may allow more confident interpretation of TSC data.