Test of Hubbard–Onsager–Felderhof’s dielectric friction theory for ion rotation in solution

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Abstract
Hubbard–Onsager–Felderhof’s (HOF) dielectric friction theory for rotational motion of ions is tested by using NMR orientational relaxation times recently measured for such polyatomic ions as ClO−4,SO2−4,PO3−4, etc. in D2O and CD3OD at infinite dilution. The HOF theory combined with the bulk solvent properties is qualitatively successful in explaining how rotational friction coefficients for ions with a high surface charge density depend on ion size and valence, temperature, and solvent. In the case of a low surface charge density, the continuum model shows its inherent limitations in the treatment of ion dynamics, rotational or translational. It turns out that the HOF theory serves an important theoretical framework for the interpretation of the semiempirical relation between orientational relaxation times of ions and the solvent viscosity divided by temperature.