Considering previous studies on the high-pressure phases and compressibility of Ba–Au alloys with stoichiometries Au
2Ba, AuBa, and Au
2Ba
3, the concentration of the alkaline-earth metal Ba increased, and a particle-swarm optimization algorithm was employed to conduct comprehensive structure
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Considering previous studies on the high-pressure phases and compressibility of Ba–Au alloys with stoichiometries Au
2Ba, AuBa, and Au
2Ba
3, the concentration of the alkaline-earth metal Ba increased, and a particle-swarm optimization algorithm was employed to conduct comprehensive structure searches for the Ba
4Au compound at 0, 10, 20, and 50 GPa. First-principles calculations were subsequently carried out to investigate its structural evolution and electronic properties under compression. Enthalpy-difference calculations indicate that the
I4
/mmm phase of Ba
4Au transforms to the
Cmmm phase at approximately 0.4 GPa. As pressure increases above 5.7 GPa, the
I4
/m structure becomes energetically more favorable than
Cmmm-Ba
4Au, indicating that the
Cmmm phase transforms to the
I4
/m phase at 5.7 GPa. Both phase transitions are first-order and accompanied by discernible volume collapses. Additionally, a comparative analysis of the electronic properties of Ba
4Au was performed before and after the phase transitions. In this study, theoretical guidance is provided for the exploration of the high-pressure structural evolution of Ba
4Au, and critical insights are offered regarding the changes that occur in its physical and chemical properties under compression.
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