Negative Thermal Expansion in Cuprite-Type M2X (M = Cu, Ag, Au; X = O, S): A Quasi-Harmonic Lattice Dynamics Study

IF 8.7 1区化学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

ACS Materials Letters Pub Date : 2025-08-14 DOI:10.1021/acsmaterialslett.5c00793

Yuchao Li, Zhengli Liang, Youquan Liu, Qin Chen, Ran Zhang, Xingxing Jiang*, Martin T. Dove and Zheshuai Lin*,

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Abstract

Understanding the mechanisms of negative thermal expansion (NTE) in solids is crucial for controlling this anomalous thermal response. In this work, we investigate NTE in the cuprite-type M₂X family (M = Cu, Ag, Au; X = O, S) by first-principles quasi-harmonic lattice dynamics simulations. Au₂S has a much more pronounced NTE effect than Cu₂O and Ag₂O in experimentally available structures, while the predicted Cu₂S exhibits the most pronounced NTE response within this family. Their predicted NTE is dominated by low-frequency optical and transverse phonon modes, which drives the deformation of [XM₄] tetrahedra, and arises from the competition between transverse and longitudinal vibrations in bridging atoms. Notably, we establish a characteristic ratio of transverse to longitudinal vibration permissibility that shows nearly linear correlation with NTE magnitude across this family. This work clarifies structure–property relationships for NTE in cuprite-type materials and reveals fundamental insights to guide the development of NTE materials.

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铜型M2X （M = Cu, Ag, Au; X = O， S）的负热膨胀：准调和晶格动力学研究

了解固体中负热膨胀（NTE）的机制对于控制这种异常热响应至关重要。在这项工作中，我们通过第一性原理拟调和晶格动力学模拟研究了铜型M2X族（M = Cu, Ag, Au; X = O， S）中的NTE。在实验结构中，Au2S比Cu2O和Ag2O具有更明显的NTE效应，而预测的Cu2S在该家族中表现出最明显的NTE响应。他们预测的NTE由低频光学和横向声子模式主导，这驱动了[XM4]四面体的变形，并且产生于桥接原子中横向和纵向振动之间的竞争。值得注意的是，我们建立了横向与纵向振动允许度的特征比，显示出与整个家族的NTE强度几乎线性相关。这项工作澄清了铜型材料中NTE的结构-性能关系，并揭示了指导NTE材料发展的基本见解。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ACS Materials Letters MATERIALS SCIENCE, MULTIDISCIPLINARY-

CiteScore

14.60

自引率

3.50%

发文量

261

期刊介绍： ACS Materials Letters is a journal that publishes high-quality and urgent papers at the forefront of fundamental and applied research in the field of materials science. It aims to bridge the gap between materials and other disciplines such as chemistry, engineering, and biology. The journal encourages multidisciplinary and innovative research that addresses global challenges. Papers submitted to ACS Materials Letters should clearly demonstrate the need for rapid disclosure of key results. The journal is interested in various areas including the design, synthesis, characterization, and evaluation of emerging materials, understanding the relationships between structure, property, and performance, as well as developing materials for applications in energy, environment, biomedical, electronics, and catalysis. The journal has a 2-year impact factor of 11.4 and is dedicated to publishing transformative materials research with fast processing times. The editors and staff of ACS Materials Letters actively participate in major scientific conferences and engage closely with readers and authors. The journal also maintains an active presence on social media to provide authors with greater visibility.