Universal Framework for Decomposing Ionic Transport into Interpretable Mechanisms

TL;DR

This paper introduces a computational framework that decomposes ion transport in materials into interpretable mechanisms, providing detailed insights into microscopic events and their contributions to macroscopic conductivity.

Contribution

The framework offers a novel, quantitative method to analyze MD trajectories, linking microscopic transitions to overall transport coefficients with interpretability and reproducibility.

Findings

Resolved debates on concerted motion and exchange mechanisms

Identified dominant ion transport pathways and rate-limiting steps

Quantified activation energies for different transport modes

Abstract

Understanding mechanisms of ion transport in bulk materials is central to designing next-generation ion conductors for energy storage devices, yet studies employing all-atom molecular dynamics (MD) have largely been limited to reporting overall transport coefficients without a quantitative, spatiotemporally resolved breakdown of \emph{how} charge is carried. We present a computational framework that analyzes MD trajectories to quantitatively interpret macroscopic transport by decomposing it into additive contributions from physically motivated events. They are defined either through heuristically identified microscopic transitions, capturing events such as single-ion hops, multi-ion hops, and vehicular motion, or through transitions between chemically interpretable coordination macrostates. The construction guarantees that attributed contributions sum exactly to the Onsager transport coefficients estimated via the Green-Kubo/Einstein formalism, while scanning the sampling window exposes characteristic temporal scales at which distinct transport mechanisms emerge and dominate. Applied across three prototypical electrolytes-inorganic crystals, liquids, and polymers-the framework quantitatively resolves long-standing debates (e.g., the role of concerted motion and exchange), identifies dominant mechanisms and rate-limiting steps, quantifies their frequencies and effectiveness, and extracts activation energies for distinct transport modes, thereby distilling design rules for fast conduction. This general and reproducible analysis tool turns MD trajectories into quantitative mechanism maps, enabling the ion-conductor community to adjudicate mechanistic hypotheses and accelerate discovery.