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

Fuente: arXiv
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Main Authors: Hao, Daxue, Huang, Hao, Li, Geng, Wu, Yu, Zeng, Shuming
Format: Preprint
Published: 2026
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author Hao, Daxue
Huang, Hao
Li, Geng
Wu, Yu
Zeng, Shuming
author_facet Hao, Daxue
Huang, Hao
Li, Geng
Wu, Yu
Zeng, Shuming
contents 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 ($κ_L$). Crucially, non-equilibrium simulations reveal a pronounced non-monotonic anomaly in $κ_L$ near the phase transition, deviating from the conventional $\sim 1/T^α$ 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.
format Preprint
id arxiv_https___arxiv_org_abs_2603_23851
institution arXiv
publishDate 2026
record_format arxiv
spellingShingle Coupling of phase transition, anharmonicity, and thermal transport in CaSnF$_6$
Hao, Daxue
Huang, Hao
Li, Geng
Wu, Yu
Zeng, Shuming
Materials Science
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 ($κ_L$). Crucially, non-equilibrium simulations reveal a pronounced non-monotonic anomaly in $κ_L$ near the phase transition, deviating from the conventional $\sim 1/T^α$ 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.
title Coupling of phase transition, anharmonicity, and thermal transport in CaSnF$_6$
topic Materials Science
url https://arxiv.org/abs/2603.23851