Proton dynamics in the perchloric acid clathrate hydrate HClO4.5.5H2O

In the perchloric acid clathrate hydrate HClO4.5.5H2O, the perchlorate anions are contained inside an aqueous host crystalline matrix, positively charged because of the presence of delocalized acidic protons. Our experimental results demonstrate that the microscopic mechanisms of proton conductivity in this system are effective on a time scale ranging from nanosecond to picosecond. In the present paper, we discuss more specifically on the relaxation processes occurring on a nanosecond time scale by combining high-resolution quasielastic neutron scattering and 1H pulse-field-gradient nuclear magnetic resonance experiments. The combination of these two techniques allows us to probe proton dynamics in both space and time domains. The existence of two types of proton dynamical processes has been identified. The slowest one is associated to long-range translational diffusion of protons between crystallographic oxygen sites and has been precisely characterized with a self-diffusion coefficient of 3.5 x 10(-8) cm2/s at 220 K and an activation energy of 29.2+/-1.4 kJ/mol. The fastest dynamical process is due to water molecules' reorientations occurring every 0.7 ns at 220 K with an activation energy of 17.4+/-1.5 kJ/mol. This powerful multitechnique approach provides important information required to understand the microscopic origin of proton transport in an ionic clathrate hydrate.