First-principles molecular dynamics simulation(FPMD) has been applied to study the ionic structure and electronic properties of Na₃AlF₆ molten salt. The results show that the main forms of complex ion groups in molten salt are [AlF₄]⁻, [AlF₅]²⁻ and [AlF₆]³⁻, with the proportion of 10%, 60% and 30%, respectively. The electron orbitals near Fermi level are mainly occupied by F-2p and hybridize with Al-3p orbitals, in which electrons are transferred from Al-3p orbitals to F-2p orbitals. The calculation results of Raman spectra on [AlF₄]⁻, [AlF₅]²⁻ and [AlF₆]³⁻ are close to the experimental values, indicating FPMD is applicable to similar molten salt systems.

应用第一性原理分子动力学模拟（FPMD）研究了Na ₃ AlF ₆熔盐的离子结构和电子性质。结果表明，熔盐中复合离子基团的主要形式为[AlF ₄ ] ^-，[AlF ₅ ] ^2-和[AlF ₆ ] ^3-，所占比例分别为10％，60％和30％。费米能级附近的电子轨道主要被F-2p占据并与Al-3p轨道杂化，其中电子从Al-3p轨道转移到F-2p轨道。[AlF ₄ ] ^-，[AlF ₅ ]的拉曼光谱的计算结果^2-和[AlF ₆ ] ^3-接近实验值，表明FPMD适用于类似的熔盐体系。