Probing anharmonic and heterogeneous carrier dynamics across sublattice melting in a minimal model superionic conductor

Abstract

Despite decades of research, the microscopic origin of sublattice melting and fast ion transport in superionic conductors remains elusive. Here, we introduce a chemically neutral minimal binary model consisting of a rigid host lattice stabilized by short-range steric repulsion and a soft carrier sublattice interacting via long-range Wigner-type forces. This contrast naturally produces distinct melting temperatures and an intermediate sublattice-melting phase in which carriers become fluidlike while the host remains crystalline. Molecular dynamics simulations identify multiple dynamical regimes–crystalline, sublattice-melt, and fully molten–marked by sharp changes in diffusivity, structural correlations, and dynamical heterogeneity. Near sublattice melting, carrier motion is strongly anharmonic and spatially heterogeneous, beyond mean-field hopping descriptions. By tuning the density, we demonstrate that sublattice melting can be continuously controlled, establishing a direct link between lattice softness, anharmonicity, and collective ion transport. Comparison with conventional long-range Coulombic models confirms that our minimal model reproduces the key dynamical signatures of superionicity, providing a unified microscopic foundation for designing mechanically robust superionic conductors.