Transport phenomena in superionic solids: Master equation approach

A first-principles derivation of the master equation is systematically given based on Kikuchiʹs ansatz, which is then applied to non-interacting (ideal) and interacting lattice–gas systems. The former application to an anomalous diffusion, observed by MD simulation of β-AgI, makes its mechanism clear in terms of relaxation modes such that the anomalous diffusion is due to non-diffusive (collective) modes. It is also shown in random systems that anomalous frequency-dependent conductivities, made up of Jonscher and nearly constant loss regimes, are reduced to a single master curve. The case of interacting lattice–gas system is discussed on the ab-plane of Rb3H(SeO4)2 by a pair approximation of the path probability method, where a spontaneous strain involved in the ferroelastic phase turns out to be a proton-trapped state originated in an attractive strain energy mediated by a proton–displacement interaction, and the transition to superprotonic phase is due to an off-trapping of protons. This mechanism is confirmed by no phase transition without the attractive strain energy.