An atomistic understanding of the interaction between Au clusters and dichalcogenides nanoflakes of different polytypes is fundamental to improve our knowledge to the tuning of the physical-chemical properties of hybrid dimensional composite materials. Here, we report a density functional theory investigation into the changes of structural, energetic, and electronic properties induced by the adsorption of Au₄ clusters (planar and tetrahedron) onto Mo₁₆Se₃₂ and Mo₃6Se₇2 nanoflakes of both 1T’ and 2H polytypes. We found that the Au–Se interaction plays a critical role in the nature of the Au₄/MoSe₂ interactions, in which there is a strong energetic preference for the S atoms located at the edges for all nanoflake sizes and polytypes. In summary, the Au⋯MoSe₂ binding mechanisms is composed of either (i) splitting of Se sp²-orbitals interacting with Au sd³-orbitals, or (ii) re-hybridized Au sd³ splitting of Mo $d_{z^2}$-orbitals, with low charge transfer in both due to Au₄ cluster electron filling. Furthermore, the cluster/nanoflake adsorption energetics and structural distortions due to the Au⋯MoSe₂ interactions are mainly determined by the MoSe₂ edge configurations.

对Au团簇和不同多型二卤化碳纳米薄片之间相互作用的原子学理解，对于提高我们对混合尺寸复合材料的物理化学性质进行调节的知识至关重要。在这里，我们报告密度泛函理论研究的结构，能量和电子性质的变化，由Au ₄团簇（平面和四面体）吸附到1T'和Mo的Mo ₁₆ Se ₃₂和Mo ₃ 6Se ₇ 2纳米薄片上引起的2H多型。我们发现Au-Se相互作用在Au ₄ / MoSe ₂的性质中起着至关重要的作用相互作用，其中对于所有纳米片大小和多型体，位于边缘的S原子都有强烈的能量偏好。总之，在Au⋯摩西₂结合机构是由任一（的我的Se）分裂SP ^2个-orbitals用Au相互作用SD ^3个-orbitals，或（II）重新杂交的Au SD ³分割的Mo$d_{{ž}^2}$-轨道，由于Au ₄团簇电子填充，电荷转移都很低。此外，由于Au⋯MoSe ₂相互作用引起的团簇/纳米片状吸附能和结构变形主要由MoSe ₂边缘构型决定。