Proton diffusion in the hexafluorophosphoric acid clathrate hydrate.

The hexafluorophosphoric acid clathrate hydrate is known as a "super-protonic" conductor: its proton conductivity is of the order of 0.1 S/cm at ca. room temperature. The long-range proton diffusion and the associated mechanism have been analyzed with the help of incoherent quasi-elastic neutron scattering (QENS) and proton pulsed-field-gradient nuclear magnetic resonance ((1)H PFG-NMR). The system crystallizes into the so-called type I clathrate structure (SI) at low temperature and into the type VII structure (SVII) above ca. 230 K with a melting point close to room temperature. While, in the SI phase, no long-range proton diffusion is observed (at least faster than the present measurement capabilities, i.e., 10(-7) cm(2)·s(-1)) with respect to the probed time scale, both techniques evidence a long-range proton diffusion process in the SVII phase (3.85 × 10(-6) cm(2)·s(-1) at 275 K with an activation energy of 0.19 ± 0.04 eV). QENS experiments lead to modeling the microscopic mechanism of the long-range proton diffusion by means of a Chudley-Elliot jump diffusion model with a characteristic jump distance of 2.79 ± 0.17 Å. In other words, the long-range diffusion occurs through a Grotthus mechanism with proton jumping from one water-oxygen site to another. Moreover, the analysis of the proton diffusion for hydration numbers greater than 6 (i.e., in the SVII structure) reveals that the additional water molecules coexisting with the SVII structure act as a "structural defect" barrier for the proton diffusivity, responsible for the conductivity.