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Magnetic resonance line-shape and relaxation time studies of rotational diffusion in liquids Phillips, Paul Stewart


A new numerical analysis method, dispersion vs. absorption plots (DISPA), has been developed for ESR. This method may be used for semi-quantitative line-shape studies and is useful both as a diagnostic and analytical tool. In addition it provides a method of automatic phasing for magnetic resonance spectra. Numerous examples of its applications, both simulated and experimental are presented, with emphasis on spin-probe studies. The digital acquisition and processing methods used for these studies are also briefly discussed. ESR and NMR relaxation time studies of the bis(dialkyl-N-carbodithioate) metal(II) class of spin-probes have been performed. The T₁,'s of ¹³C and ²H enriched nickel complex were measured by NMR. The line-widths of ⁶³Cu complex were measured by ESR and analysed by Redfield theory. The two sets of results were combined to give the principal elements of the rotational diffusion tensor for the pyrollidine derivative in toluene. This is the first time that ESR and NMR studies have been combined to measure a diffusion tensor. A general strategy for this approach is presented. ESR data from previous work has been re-analysed in the light of the new results. The analysis shows that the commonly used assumption of isotropic diffusion is extremely misleading.

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