Coupling of phase transition, anharmonicity, and thermal transport in CaSnF$_6$

Abstract

Understanding the coupling between structural phase transitions and thermal transport is essential for designing functional materials with tunable properties. Here, we investigate this interplay in CaSnF$_6$ by combining first-principles calculations with a machine-learned neuroevolution potential that enables large-scale molecular dynamics simulations across a wide temperature range. The simulations accurately capture the first-order structural phase transition and associated lattice dynamics. We show that the negative thermal expansion originates from low-energy rigid unit modes involving cooperative rotations of corner-sharing [CaF$_6$]$^{4-}$ octahedra, which induce bond-angle bending and volume contraction. At the same time, strong anharmonicity, dominated by four-phonon scattering, plays a central role in suppressing lattice thermal conductivity ($\kappa_L$). Crucially, non-equilibrium simulations reveal a pronounced non-monotonic anomaly in $\kappa_L$ near the phase transition, deviating from the conventional $\sim 1/T^{\alpha}$ behavior and providing direct transport evidence of lattice reconstruction. These results establish a unified mechanism linking lattice geometry, anharmonic vibrational dynamics, and thermal transport, and highlight the potential of machine-learned potentials for bridging atomic-scale phase transitions with macroscopic transport properties.