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元素镁和铝是地壳中丰度较高且被广泛应用于工业工程中的金属材料，它们在高压下能以单质形式形成电子化合物，导致丰富多彩的晶体结构和电子性质。本研究使用第一性原理结构搜索方法系统地对0-500GP压力范围内镁铝合金的可能结构进行了探索，获得了8种可在不同压强范围下稳定存在的晶体结构和2种亚稳的富镁合金结构，其中6种稳定结构具有电子化合物特征。通过计算分析验证了电子化合物中间隙准原子对晶格振动特性的影响，同时在富镁合金结构中发现铝原子具有独特的-5e超高氧化价态，形成满壳层电子结构。本研究丰富了镁铝合金的高压相图，并为开发新型高压功能材料提供了理论参考。Magnesium and aluminum are abundant metals in the Earth's crust and are widely utilized in industrial engineering. Under high pressure, these elements can form elemental compounds as single substances, leading to a variety of crystal structures and electronic properties. This study systematically investigated the possible structures of magnesium-aluminum alloys within the pressure range of 0-500 GPa using the first-principles structure search method, with energy and electronic structure calculations conducted using the VASP package. Bader charge analysis characterized atomic and interstitial quasiatom (ISQ) valence states, while lattice dynamics were analyzed using the PHONOPY package via the small-displacement supercell approach. Eight stable phases (MgAl3-Pm-3m、 MgAl3-P63/mmc、 MgAl-P4/mmm、 MgAl-Pmmb、 MgAl-Fd-3m、 Mg2Al-P-3m1、 Mg3Al-P63/mmc、 Mg3Al-Fm-3m) and two metastable phases (Mg4Al-I4/m、 Mg5Al-P-3m1) were identified. The critical pressures and stable intervals for phase transitions were precisely determined. Notably, MgAl-Fd-3m、 Mg2Al-P-3m1、 Mg4Al-I4/m and Mg5Al-P-3m1 represent newly predicted structures. Analysis of electronic localization characteristics revealed that six stable structures (MgAl3-Pm-3m 、 MgAl3-P63/mmc 、 MgAl-Pmmb 、 MgAl-Fd-3m 、 Mg2Al-P-3m1 and Mg3Al-P63/mmc) exhibit electronic properties of electrides. Interstitial quasi-atoms (ISQs) primarily originate from charge transfer of Mg atoms. In the metastable phase Mg4Al-I4/m, it was predicted that Al atoms achieve an Al5- valence state, filling the p shell. This finding demonstrates that by adjusting the Mg/Al ratio and pressure conditions, a transition from traditional electrides to high negative valence states can be realized, offering new insights into the development of novel high-pressure functional materials. Furthermore, all Mg-Al compounds display metallic behavior, with their stability attributed to Al-p-d orbital hybridization, which significantly contributes to the Al-3p/3d orbitals near the Fermi level. Additionally, LA-TA splitting was observed in MgAl3-Pm-3m, with a splitting value of 45.49 cm-1, confirming the unique regulatory effect of ISQs on lattice vibrational properties. These results elucidate the rich structural and electronic properties of magnesium-aluminum alloys as electrides, providing deeper insights into their behavior under high pressure and inspiring further exploration of structural and property changes in high-pressure alloys composed of light metal elements and p-electron metals.
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Keywords:
- magnesium-aluminum alloys /
- high-pressure structure and phase transition /
- electrides /
- density functional theory
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