Abstract: Conventional barocaloric materials typically exhibit limited operating temperature ranges. In contrast, KPF₆ has recently been reported to achieve an exceptional all-temperature barocaloric effect (BCE) via pressure-driven phase transitions. Here, we elucidate the atomistic mechanisms underlying the phase transitions through first-principles calculations and machine-learning potential accelerated molecular dynamics simulations. We identify four distinct phases: the room-temperature cubic (C) plastic crystal characterized by strong fluorine orientational disorder (FOD) and anharmonicity, the intermediate-temperature monoclinic (M-II) phase with decreasing FOD, the low-temperature monoclinic (M-I) phase with suppressed FOD, and the fully ordered rhombohedral (R) phase under pressure. Phonon calculations confirm the dynamic stability of the M-II, M-I, and R phases at 0 K, whereas the C phase requires thermal fluctuations for stabilization. Under pressure, all the C, M-II, and M-I phases transform to the R phase, which are driven by cooperative PF₆ octahedral rotations coupled with lattice modulations. These pressure-induced phase transitions result in persistent isothermal entropy changes across a wide temperature range, thereby explaining the experimentally observed all-temperature BCE in this material. This work deciphers the interplay between FOD, anharmonicity, and phase transitions in KPF₆, providing important insights for the design of BCE materials with broad operational temperature spans.

Key words: First-principles calculations, Machine-learning potential, Molecular dynamics simulations, Phase transitions, Barocaloric material, KPF6