Isotopic Fingerprints of Proton-Mediated Dielectric Relaxation in Solid and Liquid Water

We report cross-validated measurements of the isotope effect on dielectric relaxation for four isotopologues of ice and water, including the 1-10^5 Hz region, in which only sporadic and inconsistent measurements were previously available. In ice, the relaxation rates exhibit an activated temperature dependence with an isotope-independent activation energy. Across 248-273 K, the H₂O-to-D₂O relaxation rate ratio remains constant at 2. 0±0. 1. This scaling agrees with Kramers' theory in the high-friction limit if the moving mass is the proton or deuteron, indicating that dielectric relaxation is governed by a classic proton transfer over an energy barrier rather than molecular reorientation.