On the Novel Structure and Metallization of Hydrogen under High Pressure
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摘要: 在极端压缩状态下，氢呈现出丰富的物理及化学变化，其结构与相图揭示了凝聚态物质高压行为的典型特征，在天体物理和新材料研究中有重要应用。本文简要回顾了金属氢概念的提出，以及直至最近几年的研究进展，分析总结了高密度氢研究中的一些核心问题和发展态势。利用密度泛函理论计算和状态方程模型分析，综合探讨了氢在高压下复杂的原子结构、分子氢离解区域附近的复杂行为、金属氢的亚稳定性和可回收性，以及“DAC+冲击”加载方法在金属氢研究中的优势与不足等问题。结果表明：通过快速或缓慢的压力释放回收金属氢的高压相到常压是几乎不可能的；高压下氢的复杂行为给实验和理论研究带来了巨大挑战，特别是离解区域附近理论与理论、实验与实验、以及理论与实验之间的结果都存在巨大差异，暗示当前通用的实验测试方法和常用的多电子理论计算方法还存在很大的改进空间。Abstract: Hydrogen under extremely compressed conditions exhibits extraordinary richness in physics and chemistry.Its structural transitions and phase diagram are fundamental for understanding the high pressure behavior of condensed matters, and also for important applications in astrophysics and material science.In this paper, we reviewed the research progress on metallic hydrogen since it was proposed until to very recent years.Several key issues and possible future progress about dense hydrogen are analyzed and summarized.With density functional theory calculations and a model analysis using an equation of states, we explored and demonstrated:(1)the complex and novel atomic structures of dense hydrogen; (2)the novel behaviors of hydrogen molecules near the dissociation region; (3)the stability of metallic hydrogen under pressure and the possibility of recovery to zero pressure; (4)the advantages and disadvantages of the "DAC+shock" experimental method to achieve metallic hydrogen.Our results showed that it is impossible to quench the high pressure phases of metallic hydrogen to ambient conditions.The complex behaviors of dense hydrogen present as a great challenge for both experimental and theoretical studies, especially near the dissociation of hydrogen molecules, where sharp discrepancies were unveiled, implying that much effort is still required to improve the state-of-the-art experimental and many-body theoretical methods.
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图 1 第一原理分子动力学预测的介于固体和液体之间的新奇物态——流动固体，高密度氢极有可能进入这一相态
Figure 1. The novel mobile solid state predicted by first principle molecular dynamics simulations (Dense hydrogen may transition into this state.)
图 2 介于固体与液体之间的流动固体在压力-温度(p-T)相图上的位置
Figure 2. Possible location of the mobile solid state in the p-T phase diagram
图 3 高温高压下氢的相图，离解线具体位置仍有争议
Figure 3. Phase diagram of hydrogen at high pressure and high temperature (The location of the dissociation curve is still under debate.)
图 4 DFT计算得到的沿一系列等温线的结合能-压力变化曲线
Figure 4. Predicted cohesive energy as a function of pressure along different isotherms for dense liquid hydrogen by DFT calculations
图 5 DFT计算得到的沿一系列等温线的压力-体积变化曲线
Figure 5. Pressure-volume curves of dense liquid hydrogen along different isotherms calculated by DFT
图 6 晶胞可变NEB方法预测含有H3单元或分子/原子混合相的结构在零压下具有能量平台
Figure 6. Flat landscape of energy along the NEB path for the structures containing H3 units or hydrogen molecule/atom mixture at 0GPa predicted by the cell-variable NEB method
图 7 基于DFT-PBE近似的第一原理分子动力学模拟得到的Fddd结构金属氢在低压下的过热极限
Figure 7. Superheating limit of metallic hydrogen in the Fddd structure at low pressure simulated by molecular dynamics with DFT-PBE method
图 8 晶胞可变NEB方法计算得到的315GPa压力下Fddd结构金属氢与分子晶体间的势垒
Figure 8. Energy barriers between the Fddd structure of metallic hydrogen and the molecular crystal structure at 315GPa calculated by cell-variable NEB method
图 9 CML状态方程预估的高密度氢中的“预压+冲击”路径(Tm为熔化温度)
Figure 9. Hugoniot of precompressed hydrogen predicted by the CML-EOS model (Tm:melting temperature)
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