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高压高温下MnF的结构相变与歧化反应

Structural Phase Transition and Disproportionation of MnF Under High Pressure and High Temperature.

作者信息

Liu Jie, Zhu Jinming, Yu Hongyu, Yao Andong, Zhang Zihan, Guan Rongshu, Bao Kuo, Cui Tian

机构信息

State Key Laboratory of Superhard Materials, College of Physics, Jilin University, Changchun 130012, China.

School of Physical Science and Technology, Ningbo University, Ningbo 315211, China.

出版信息

Inorg Chem. 2024 Aug 26;63(34):16114-16119. doi: 10.1021/acs.inorgchem.4c02948. Epub 2024 Aug 15.

Abstract

Materials that once suffered under high-pressure and high-temperature conditions often display unusual phenomena that challenge traditional understanding. MnF, an intermediate valence state Mn-F compound, exhibits a distorted octahedral crystal structure influenced by the Jahn-Teller effect. Here we report the structural phase transition and self-disproportionation of MnF under high pressure and high temperature. The initial octahedra phase 2/-MnF transforms into the hendecahedra phase under high pressure. Subsequently, we found that molten -MnF self-disproportionate into MnF and MnF with the aid of laser heating at a pressure above 57.1 GPa. Raman spectra and UV-vis absorption experiments confirmed these changes that were ultimately confirmed by synchrotron radiation XRD. The equation of states for the volume with the pressure of these Mn-F compounds was also given. This work expands the study of Mn-F systems and provides guidance for the behavior of transition metal fluorides under high pressures and high temperatures.

摘要

曾经在高压和高温条件下承受作用的材料常常展现出挑战传统认知的异常现象。MnF,一种中间价态的Mn-F化合物,呈现出受 Jahn-Teller 效应影响的扭曲八面体晶体结构。在此我们报告了 MnF 在高压和高温下的结构相变和自歧化反应。初始的八面体相γ-MnF在高压下转变为十一面体相。随后,我们发现在高于57.1 GPa 的压力下,借助激光加热,熔融的γ-MnF 会自歧化为 MnF₂ 和 MnF₃。拉曼光谱和紫外可见吸收实验证实了这些变化,最终通过同步辐射 X 射线衍射得到确证。还给出了这些 Mn-F 化合物的体积与压力的状态方程。这项工作拓展了对 Mn-F 体系的研究,并为过渡金属氟化物在高压和高温下的行为提供了指导。

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