Lattice Dynamics of Mercury under High Pressure
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摘要: 汞作为一种具有特殊理化性质的金属，其晶体结构及原子间相互作用在高压下会发生显著改变。然而，目前对汞在高压条件下的振动性质仍缺乏系统性实验研究，其高压相变机制仍需进一步探究。为此，依托低波数高压共聚焦拉曼光谱系统，结合金刚石对顶砧高压原位测量技术与第一性原理计算方法，系统探究了汞在高压条件下的结构相变行为及振动模式演化规律。成功获得了汞在2种高压固态相中的拉曼振动信号，揭示了其振动频率随压力的变化特征，并据此计算了相关的热力学参数。研究结果有效填补了长期以来汞的实验数据空白，为系统阐明汞高压诱导相变的物理机制奠定了关键实验基础。Abstract: Mercury is a metal with special physical and chemical properties. High pressure can significantly alter its crystal structures and interatomic interactions. However, vibration-related experimental data of mercury under high pressure have been scarce for a long time, which limits the in-depth understanding of its high-pressure phase transition mechanisms. To fill this research gap, this study systematically investigate the structural transformations and evolution of vibrational mode of mercury under high pressure. This was achieved by integrating low-wavenumber high-pressure confocal Raman spectroscopy, in-situ diamond anvil cell (DAC) techniques, and first-principles calculations. The study successfully detected the vibrational signals of two solid phases of mercury under high pressure for the first time, revealed the characteristics of pressure-dependent vibrational frequencies, and further calculated the relevant thermodynamic parameters of the two phases. The experimental data is highly consistent with the reported structural phase transitions of mercury, filling the long-standing experimental gap in this field and providing key experimental support for an in-depth understanding of the phase transition behaviors and related mechanisms of mercury under high pressure.
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图 2 低波数共聚焦拉曼光谱测试系统光路图
Figure 2. Optical path diagram of low-wavenumber confocal Raman spectroscopy system
图 4 γ-Hg拉曼模式的原子振动示意图：(a) 低频Ag振动模式，(b) 高频Ag振动模式，(c) Bg振动模式
Figure 4. Illustration of atomic vibrations for the Raman modes of γ-Hg: (a) low frequency Ag vibration mode; (b) high frequency Ag vibration mode; (c) Bg vibration mode
图 5 δ-Hg 的E2g拉曼模式原子振动示意图
Figure 5. Illustration of atomic vibrations for the E2g Raman mode of δ-Hg
图 6 20 GPa时γ-Hg的声子谱（红色虚线代表具有拉曼活性的振动模）
Figure 6. Phonon spectrum of γ-Hg at 20 GPa (The red dashed lines denote the Raman-active vibrational modes.)
图 7 γ-Hg和δ-Hg的拉曼频移随压力的变化关系
Figure 7. Pressure dependence of Raman shift of γ-Hg and δ-Hg
图 8 (a) 34.5 GPa时Hg的拉曼光谱拟合，(b) 不同压力下Bg拉曼模式峰的积分面积占比
Figure 8. (a) Raman spectrum fitting of Hg at 34.5 GPa; (b) proportion of integrated intensity of Bg Raman modes at different pressures
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