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The role of average atomic volume in predicting negative thermal expansion: The case of REFe(CN)6

平均原子晶格体积在预测负热膨胀材料中的作用: 以REFe(CN)6 为例


面对高精尖仪器或设备的热膨胀控制的需求, 探索新的负热膨胀材料显得尤为重要. 本文采用“平均原子晶格体积”概念预测各向异性新的负热膨胀材料体系, 据此发现了REFe(CN)6 (RE = La, Sm, Ho,Lu) 负热膨胀材料家族. 我们采用原位中子粉末衍射(NPD)、X射线吸收精细结构谱(EXAFS)和第一性原理计算揭示了其负热膨胀来源于低频声子振动模式中的CN原子的横向热振动, 进一步发现“平均原子晶格体积”越大, 其对应的低频声子模式频率越低, 格林艾森常数越负,CN原子的横向热振动越强. 本工作为定性预测负热膨胀材料提供了新的方法, 对热膨胀控制与设计具有重要意义.


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This work was supported by the National Natural Science Foundation of China (22071221, 21905252, 21825102 and 11774078), the Natural Science Foundation of Henan Province (212300410086) and the Innovation Scientists and Technicians Troop Construction Projects of Henan Province (10094100510025). All calculations were supported by the National Supercomputing Center in Zhengzhou. ELETTRA Synchrotron is acknowledged for providing beamtime at the XAFS beamline (Experiment n. 20185177). We thank Luca Olivi and Simone Pollastri for technical assistance.

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Correspondence to Qilong Gao or Jun Chen.

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Author contributions

Gao Q and Chen J conceived the idea and designed the experiments. Gao Q prepared the samples and performed the measurements. Sanson A analyzed and discussed the data of the X-ray absorption fine structure experiments. Sun Q performed density functional theory (DFT) calculations. Huang Q assisted in the neutron powder diffraction experiments. All authors contributed to the discussions. Gao Q and Chen J wrote the manuscript with help for the revision from all coauthors.

Conflict of interest

The authors declare that they have no conflict of interest.

Qilong Gao is currently an associate professor at Zhengzhou university (ZZU). He received his PhD degree from the Department of Physical Chemistry, University of Science and Technology Beijing (USTB). He received the award of the Excellent Youth Foundation of Henan province in 2020. Currently, he concentrates on exploring the NTE mechanism, controlling thermal expansion, and finding new NTE materials, such as Prussian blue analogues, oxides, cyanides and metal-organic frameworks by means of synchrotron radiation technology.

Jun Chen is currently a full professor at USTB, China. He received his PhD degree in Metallurgical Physical Chemistry from USTB in 2007. In 2008–2009, he was financially supported by the Alexander von Humboldt Fellowship for the research in the field of electrical ceramics at TU-Darmstadt, Germany. He visited the Structures Laboratory of the Tokyo Institute of Technology, Japan, as a foreign guest professor in 2015, and visited the Department of Physics and Astronomy of University of Padova, Italy as a visiting scientist in 2018. His current research interests include crystal structures, correlations with physical or chemical properties, and new materials design for ferroelectric, piezoelectric, magnetic, and negative thermal expansion solids.

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Gao, Q., Sun, Q., Venier, A. et al. The role of average atomic volume in predicting negative thermal expansion: The case of REFe(CN)6. Sci. China Mater. (2021).

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