Field-dependent paramagnetic relaxation enhancement in solutions of Ni(II): What happens above the NMR proton frequency of 1 GHz?

An extended set of paramagnetic relaxation enhancement (PRE) data, up to the field of 32.9 Tesla, is reported for protons in an acidified aqueous solution of a Ni(II) salt in the presence and in the absence of added glycerol. For the 55% w/w glycerol sample, a distinct maximum in the PRE vs magnetic field curve is observed for the first time. The data are analysed using the Swedish slow-motion theory, including both the intramolecular (inner-sphere) and intermolecular (outer-sphere) contributions. The results indicate that estimating the outer-sphere part in the presence of the more efficient inner-sphere term is a difficult task.