Microscopic Theory of Superionic Phase Transitions: Nonadiabatic Dynamics and Many-Body Effects

TL;DR

This paper develops a unified microscopic theoretical framework incorporating nonadiabatic dynamics and many-body effects to explain superionic phase transitions, aligning with experimental observations.

Contribution

It introduces a general lattice model that captures both normal and superionic conductors, highlighting the roles of concerted-hopping and Coulomb interactions.

Findings

Model reproduces key experimental observations.

Identifies nonadiabatic hopping as driving type-I transitions.

Highlights Coulomb interactions as key for type-II transitions.

Abstract

Superionic phase transitions have attracted extensive interest for decades due to their promising applications and rich underlying physics. In particular, complicated many-body effects and nonadiabatic dynamics are believed to play essential roles, limiting the explanatory power of phenomenological approaches and obscuring the microscopic mechanisms at play. In this work, we develop a unified theoretical framework for describing solid-state ionic conduction. After reviewing the conventional approximations, we construct a general lattice model that applies to both normal ionic and superionic conductors. By incorporating the nonadiabatic concerted-hopping mechanism and the many-body Coulomb interaction within a self-consistent mean-field scheme, we identify these two effects as the fundamental driving forces behind type-I and type-II superionic phase transitions, respectively. Our model directly reproduces key experimental observations. Within this unified framework, we further provide a comprehensive comparison between the two types of transitions. Overall, our work offers microscopic insight into superionic phase transitions and provides guidance for the design and optimization of advanced solid-state ionic conductors.