Picosecond water dynamics adjacent to charged paramagnetic ions measured by magnetic relaxation dispersion.

Measurements of water-proton spin-lattice relaxation rate constants as a function of magnetic field strength [magnetic relaxation dispersion (MRD)] in aqueous solutions of paramagnetic solutes reveal a peak in the MRD profile. These previously unobserved peaks require that the time correlation functions describing the water-proton-electron dipolar coupling have a periodic contribution. In aqueous solutions of iron(III) ion the peak corresponds to a frequency of 8.7 cm-1, which the authors ascribe to the motion of water participating in the second coordination sphere of the triply charged solute ion. Similar peaks of weaker intensity in the same time range are observed for aqueous solutions of chromium(III) chloride as well as for ion pairs formed by ammonium ion with trioxalatochromate(III) ion. The widths of the dispersion peaks are consistent with a lifetime for the periodic motion in the range of 5 ps or longer.