Pair correlation effects for attractive ions in paramagnetic D2O solutions: T1 frequency dependence at low ionic concentrations

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Abstract
We report careful measurements of the relaxation times T1 of the protons and phosphorus nuclei on the (CH3)4P+ ions in the presence of .ON(SO3)22- anion radicals in D2O solutions at 25 ○C. The measurements were repeated for several NMR frequencies and various radical concentrations up to 0.08 mol.l-1. The interpretation of the results is performed using an ion-ion mean force potential which is calculated for a model of attractive hard ions in a discrete solvent of polar molecules. The relaxation times are calculated by assuming that the relative diffusion of the ions is described by a Smoluchowski equation associated with the above potential and by taking the eccentricity of the interacting spins into account. A good agreement between theory and experiment can be obtained without any adjustable parameter, but it is qualitatively suggested that the non-spherical shape of the ions should be included in the model in order to obtain a more accurate interpretation

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