Giant negative thermal expansion exceeding 1000 K in PrMnO<sub>3</sub> via synergy of local structure distortion and orbital disordering.

Qin, Feiyu; Bai, Xiaoya; Fang, Yue-Wen; Zhu, Pengli; Wang, Jun; Cheng, Pengtao; Wang, Dunhui; Hu, Lei et al. · Nat Commun · 2025

basic_science · Level V

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Abstract

Giant negative thermal expansion (NTE), defined by volumetric expansion α<sub>V</sub> <ca. -50 × 10<sup>-6</sup> K<sup>-1</sup> (volume contraction (ΔV/V) < - 0.5% within ~100 K), is rarely observed at high temperatures. Here, we report a giant NTE persisting above 1000 K (ΔV/V = - 1.7 %, 900-1100 K) in stoichiometric PrMnO<sub>3</sub> (PMON) with a peak coefficient α<sub>V</sub> = - 114 × 10<sup>-6 </sup>K<sup>-1</sup> around 1000 K. Contrastingly, oxygen-rich PrMnO<sub>3+x</sub> (PMOA) exhibits only positive thermal expansion. The origin of NTE was uncovered via synchrotron X-ray total scattering, Cs-corrected STEM, and DFT calculations. Intriguingly, PMON uniquely hosts a local symmetry breaking featured by a 3D cross-arranged network of elongated Mn-O bonds, different from the 2D planar configurations in PMOA. By correlating atomic-scale symmetry breaking and thermally activated orbital reconfiguration to macroscopic thermal responses, we establish an unconventional paradigm for engineering giant NTE at elevated temperatures.