Abstract
The magnetic proton relaxation behaviour of free radical solutions of diethylether and diethoxyethane has been studied by a nuclear-electron double resonance method. The dielectric relaxation in the solvents has also been determined from a study of the frequency dependance of the complex dielectric constant. The motional properties of the spin-carrying molecules which govern the magnetic interactions between different spin species are described by the model of randomly diffusing hard spheres. The time dependence is assumed to result from a combination of the relative translational diffusion of the spheres and the random rotational motions of complexes of spheres. Expressions and curves are given for the nuclear electron coupling parameter of dynamic nuclear polarisation and its frequency dependence. The comparison with experimental data taken at four different frequencies corresponding to magnetic fields of 15, 175, 1070 and 3230 gauss confirms the absence of scalar interactions and yields limits for the predominating translational diffusion. Correlation times at different temperatures and distances of closest approach of spins are evaluated. The dielectric studies in ether yield a single relaxation time which is attributed to the orientation of the molecule as a whole. Diethoxyethane has a spectrum of dielectric relaxation times. The dielectric relaxation times and also their activation energies are smaller than the correlation times obtained by magnetic measurements. The viscosity is more closely related to the translational diffusion of molecules than to the dielectric relaxation time. The results are discussed in terms of the different mechanisms of motion.
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