通过密度泛函理论（density functional theory，DFT）结合B3LYP/6-31g(d)基组对Al₂₄N₂₄团簇的几何电子结构进行全面优化和物理化学性质模拟分析。研究结果表明，Al₂₄N₂₄团簇的4种基态稳定结构点群依次为S₄、C₂、S₈、O；4种Al₂₄N₂₄团簇气相下既非p型输运材料，亦非n型输运材料，也不存在双极性传递性质，但是这些团簇有利于空穴传输；在优化好的Al₂₄N₂₄团簇气相结构下，研究了它们的核独立化学位移值（nuclear independent chemical shift value，NICS），由NICS得出4种同分异构体均具有芳香性；这4种同分异构体的红外和拉曼分子振动谱表明，各分子内部振动模式对红外和拉曼振动峰值的分布具有重要的影响，随着体系内八元环数量的增多，红外谱出现轻微蓝移现象，拉曼谱中未观测到此现象；特别是对称性为O的Al₂₄N₂₄分子，内部含有6个八元环，这也导致它的振动谱不同于其他三者。

The physical-chemical properties and electronic structures of Al₂₄N₂₄ were optimized using density functional theory (DFT) at the B3LYP/6-31g(d) level. The results revealed four stable ground-state structures with point groups S₄, C₂, S₈, and O for Al₂₄N₂₄ clusters. None of the Al₂₄N₂₄ clusters exhibited p-type or n-type transport behavior in the gas phase, nor did they display bipolar characteristics; however, all four clusters favored hole transport. Based on the optimized gas-phase structures, nuclear independent chemical shift (NICS) values were calculated, confirming the aromaticity of all isomers. The IR-Raman spectra of the four clusters were analyzed, revealing that the internal vibration modes of each molecule significantly influenced the distribution of IR and Raman peak values. A slight blue shift in the IR spectra was observed with an increasing number of eight-membered rings, while no such shift was detected in the Raman spectra. Notably, the Al₂₄N₂₄ molecule with O symmetry contained six eight-membered rings, leading to vibrational spectra distinct from the other three clusters.

O561

国家自然科学基金资助项目（12004276）；山西省高等学校科技创新资助项目（2023L236）。