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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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